Thin film-based energy storage devices

ABSTRACT

The disclosed technology generally relates to thin film-based energy storage devices, and more particularly to printed thin film-based energy storage devices. The thin film-based energy storage device includes a first current collector layer and a second current collector layer over an electrically insulating substrate and adjacently disposed in a lateral direction. The thin film-based energy storage device additionally includes a first electrode layer of a first type over the first current collector layer and a second electrode layer of a second type over the second current collector layer. A separator separates the first electrode layer and the second electrode layer. One or more of the first current collector layer, the first electrode layer, the separator, the second electrode layer and the second current collector layer are printed layers.

INCORPORATION BY REFERENCE TO ANY PRIORITY APPLICATIONS

Any and all applications for which a foreign or domestic priority claimis identified in the Application Data Sheet as filed with the presentapplication are hereby incorporated by reference in their entirety forall purposes.

BACKGROUND Field

The disclosed technology generally relates to energy storage devices,and more particularly to printed thin film-based or printed energystorage devices.

Description of the Related Art

Recent advances in thin film-based electronic devices such as printedelectronic devices have enabled various new forms of electronics thatare adapted increased ubiquity, higher level of integration and forpotentially lower cost. Thin film-based electronic devices includeflexible displays and electronics on three-dimensional (3D) structures,larger area electronics such as sensor arrays, higher performancedevices such as organic light emitting displays, various devices adaptedfor internet of things (IoT), wearable devices, Bluetooth® devices,light emitting devices, wireless devices (e.g., antennas for inductivecharging), radio-frequency identification (RFID), to name a few.

Some thin film-based electronic devices are connected or integrated withenergy storage devices (ESDs), such as batteries and supercapacitorsthat provide power to the electronic devices. The thin film-based energystorage devices can be fabricated and/or advantageously integrated withESDs that are also thin-film based, where the thin film-based ESDs arefabricated using similar processes used to fabricate the thin film-basedelectronic devices. For example, the thin film-based ESDs may be printedusing similar printing processes used to fabricate the printed thinfilm-based electronic devices.

To serve as suitable power sources for the thin film-based electronicdevices, the thin film-based ESDs should have compatible attributes. Forexample, some thin film-based electronic devices are adapted to beflexible devices. To be compatible with these types of devices, the thinfilm-based ESDs should also be flexible. To be compatible with a widevariety of thin film-based electronic devices having a wide range ofpower and energy needs (e.g., a capacity range such as 1-100 mAh and avoltage range such as 1.5 V-6 V), the thin film-based ESDs that powerthese devices should be configurable to meet the different needs.Furthermore, the thin film-based ESDs should deliver these performancesat a cost that is compatibly low as the thin film-based electronicdevices themselves. To meet these and other needs, there is a need forthin film-based ESDs and manufacturing processes that can provide theversatility including a wide range of capacity and output voltage,configurability, integratability, and relatively low manufacturing costand compatibility with thin film-based electronic devices.

SUMMARY

In an aspect, a method of fabricating an energy storage device includesprinting laterally adjacent and electrically separated current collectorlayers including a first current collector layer and a second currentcollector layer over a substrate. The method additionally includesprinting an electrode layer of a first type over the first currentcollector layer and printing an electrode layer of a second type overthe second current collector layer. The method further includes printinga separator over one or both of the electrode layers of the first andsecond types. Printing the separator includes printing over exposedsurfaces of one or both of the electrode layers of the first and secondtypes. The electrode layer of the first type includes a first electrodeactive material and the electrode layer of the second type includes asecond electrode active material. A molar ratio between the firstelectrode active material and the second electrode active material isbetween 0.25 and 4.0.

In another aspect, a method of fabricating an energy storage deviceincludes printing a plurality of laterally adjacent and electricallyseparated current collector layers over a substrate. The methodadditionally includes printing electrode layers of a first type over atleast a first subset of the plurality of current collector layers andprinting electrode layers of a second type over at least a second subsetof the plurality of current collector layers. The method furtherincludes printing a plurality of separator layers to form a plurality ofelectrically connected cells of the energy storage device, wherein eachof the cells comprises one separator of the plurality of separatorlayers contacting one of the electrode layers of the first type and oneof the electrode layers of the second type.

In another aspect, a manufacturing kit for an energy storage deviceincludes an unactivated energy storage device. The unactivated energystorage device includes a substrate,

a plurality of laterally adjacent and electrically separated currentcollector layers over the substrate. The plurality of current collectorlayers include a first current collector layer and a second currentcollector layer. The unactivated energy storage device additionallyincludes an electrode layer of a first type is over the first currentcollector layer, an electrode layer of a second type over the secondcurrent collector layer, and a dry separator over one or both of theelectrode layers of the first and second types. The separator includesan exposed portion through which the dry separator is configured toreceive an electrolyte. The manufacturing kit additionally includes anelectrolyte configured to be applied to the unactivated energy storagedevice to activate the energy storage device.

In another aspect, a method of fabricating an electrical system includesprinting an energy storage device over a battery-powered core deviceover a substrate. The core device is configured to receive power througha first power terminal and a second terminal and the energy storagedevice is configured to provide the power to the battery-powered coredevice. Printing the energy storage device includes printing a pluralityof current collector layers including a first current collector layerand a second current collector layer. At least one of the first orsecond current collector layers is printed over the first and secondpower terminals. Printing the energy storage device additionallyincludes printing an electrode layer of a first type over the firstcurrent collector layer, printing an electrode layer of a second typeover the second current collector layer, and printing a separator overexposed surfaces of one or both of the electrode layers of the first andsecond types.

In another aspect, an energy storage device includes a first currentcollector layer and a second current collector adjacently disposed in alateral direction over an electrically insulating substrate. The energystorage device additionally includes a first electrode layer of a firsttype over the first current collector layer, a separator over the firstelectrode layer and a second electrode layer of a second type differentfrom the first type over the separator. The second electrode layerincludes a base portion extending from the second current collectorlayer in a vertical direction and a lateral extension portion laterallyextending from the base portion in the lateral direction to laterallyoverlap the first electrode layer. One or more of the first currentcollector layer, the first electrode layer, the separator, the secondelectrode layer and the second current collector layer is printed layer.

In another aspect, an energy storage device includes a first currentcollector layer and a second current collector layer over anelectrically insulating substrate and adjacently disposed in a lateraldirection. The energy storage device additionally includes a firstelectrode layer of a first type over the first current collector layer,a second electrode layer of a second type over the second currentcollector layer, and a separator over the first electrode layer and thesecond electrode layer. One or more of the first current collectorlayer, the first electrode layer, the separator, the second electrodelayer and the second current collector layer is a printed layer. Thefirst electrode layer comprises a first electrode active material andthe second electrode layer comprises a second electrode active material,wherein a molar ratio between the first electrode active material andthe second electrode active material is between 0.25 and 4.0.

In another aspect, an energy storage device includes a first currentcollector layer over an electrically insulating substrate, a firstelectrode layer of a first type over the first current collector layer,a separator over the first electrode layer and covering a top surfaceand a side surface thereof, a second electrode layer of a second typeover the separator, and a second current collector layer comprising abase portion extending from the electrically insulating substrate in avertical direction and a lateral extension portion laterally extendingfrom the base portion in the lateral direction to overlap the secondelectrode layer. One or more of the first current collector layer, thefirst electrode layer, the separator, the second electrode layer and thesecond current collector layer are printed layers. The first electrodelayer comprises a first electrode active material and the secondelectrode layer comprises a second electrode active material. A molarratio between the first electrode active material and the secondelectrode active material is between 0.25 and 4.0.

In another aspect, an energy storage device includes an electricallyinsulating substrate and a first current collector and a second currentcollector formed over the electrically insulating substrate. The firstcurrent collector comprises a plurality of first current collectorfinger structures and the second current collector comprises a pluralityof second current collector finger structures. The first currentcollector finger structures and the second current collector fingerstructures are interleaved to alternate in a lateral direction. A firstelectrode layer of a first type is formed over the first currentcollector layer and a second electrode layer of a second type is overthe second current collector layer. A separator layer separates thefirst electrode layer and the second electrode layer.

In another aspect, an energy storage device includes a plurality oflaterally adjacent and electrically separated current collectors over anelectrically insulating substrate. The energy storage device comprises aplurality of electrically connected energy storage cells. Each of theenergy storage cells comprises a first electrode layer of a first typeon one of the current collectors, a second electrode layer of a secondtype on an adjacent one of the current collectors, and a separatorcontacting and electrically separating the first electrode layer and thesecond electrode layer.

In another aspect, a method of activating an energy storage deviceincludes providing an unactivated energy storage device. The unactivatedenergy storage device includes a substrate and a plurality of laterallyadjacent and electrically separated current collector layers over thesubstrate. The plurality of current collector layers includes a firstcurrent collector layer and a second current collector layer. Theunactivated energy storage device additionally includes an electrodelayer of a first type over the first current collector layer, anelectrode layer of a second type over the second current collectorlayer, and a dry separator over one or both of the electrode layers ofthe first and second types. The separator comprises an exposed portionthrough which the dry separator is configured to receive an electrolyte.The method additionally includes activating the energy storage device byapplying an electrolyte to the dry separator.

In another aspect, a thin film-based electronic device includes a thinfilm-based core device and a thin film-based energy storage device (ESD)electrically connected to each other. The thin film-based core deviceand the thin film-based energy storage device are integrated on a commonsubstrate and overlap each other in a direction normal to the commonsubstrate.

In another aspect, a thin film-based electronic device includes a thinfilm-based energy storage device (ESD) and a thin film-based energyharvesting device and electrically connected to the thin film-based ESDand configured to charge the thin film-based ESD. The thin film-basedenergy harvesting device and the thin film-based energy storage deviceare integrated on a common substrate.

In another aspect, a wearable thin film-based electronic device includesa plurality of laterally adjacent and electrically separated currentcollectors over an electrically insulating substrate. The deviceadditionally includes a plurality of electrically connected energystorage cells. Each of the energy storage cells comprises a firstelectrode layer of a first type on one of the current collectors, asecond electrode layer of a second type on an adjacent one of thecurrent collectors, and a separator contacting and electricallyseparating the first electrode layer and the second electrode layer. Theplurality of electrically connected energy storage cells is configuredto be worn by a user.

In another aspect, a configurable energy storage device includes aplurality of laterally adjacent and electrically separated currentcollectors over an electrically insulating substrate. The energy storagedevice comprises a plurality of electrically connected energy storagecells. The electrically connected energy storage cells are configured tobe detached from each other upon receiving a mechanical force to form apattern of electrically connected energy storage cells.

In another aspect, an energy storage device includes a plurality ofradially arranged and electrically separated current collectors over anelectrically insulating substrate. The energy storage device comprises aplurality of radially arranged and electrically connected energy storagecells. Each of the energy storage cells comprises a first electrodelayer of a first type on one of the current collectors, a secondelectrode layer of a second type on an adjacent one of the currentcollectors, and a separator contacting and electrically separating thefirst electrode layer and the second electrode layer.

In another aspect, an energy storage device includes an electricallyinsulating substrate,

a first current collector over the electrically insulating substrate anda second current collector over the electrically insulating substrate.The first current collector comprises a plurality of first currentcollector finger structures. The second current collector comprises aplurality of second current collector finger structures. The firstcurrent collector finger structures and the second current collectorfinger structures are interleaved to alternate in a lateral direction.The first and second current collectors are radially arranged such thatone of the first and second current collectors radially surrounds theother of the first and second current collectors. The deviceadditionally includes a first electrode layer of a first type over thefirst current collector layer, a second electrode layer of a second typeover the second current collector layer and a separator layer separatingthe first electrode layer and the second electrode layer.

BRIEF DESCRIPTION OF THE DRAWINGS

These and other features, aspects, and advantages of the presentdisclosure are described with reference to the drawings of certainembodiments, which are intended to illustrate certain embodiments andnot to limit the invention. In the drawings, features having referencenumerals in parenthesis indicate features that are underneath anotherfeature when viewed by the reader.

FIG. 1 illustrates a thin film-based energy storage device havingvertically stacked current collectors and electrode layers.

FIG. 2A illustrates a side view of a thin film-based energy storagedevice having laterally adjacent current collectors and electrodelayers.

FIG. 2B illustrates a plan view of electrode layers of the thinfilm-based energy storage device illustrated in FIG. 2A.

FIG. 3A illustrates a side view of a thin film-based energy storagedevice having asymmetric laterally adjacent current collectors andelectrode layers, where the ratio of surface areas between the first andsecond electrode layers is adjusted in accordance with a molar ratio ofthe active materials.

FIG. 3B illustrates a plan view of electrode layers of the thinfilm-based energy storage device illustrated in FIG. 3A.

FIG. 4 illustrates a side view of a thin film-based energy storagedevice having laterally adjacent current collectors and electrode layersthat have overlapping portions in the vertical direction.

FIG. 5 illustrates a side view of a having laterally adjacent currentcollectors and electrode layers, where the electrode layers are formedon opposing major surfaces of a perforated separator, for increasedcapacity without increasing the overall lateral footprint of the thinfilm-based energy storage device.

FIG. 6 illustrates a plan view of thin film-based energy storage deviceillustrated in FIG. 5.

FIG. 7 illustrates a side view of a thin film-based energy storagedevice having vertically stacked current collectors and electrodelayers, where one of the current collectors has perforations formedtherethrough, and has opposing major surfaces having electrode layersformed thereon, for increased capacity without increasing the overalllateral footprint of the thin film-based energy storage device.

FIG. 8 illustrates a side view of a thin film-based energy storagedevice having vertically stacked current collectors and electrodelayers, where two first electrode layers, two second electrode layersand two separators are configured as two energy storage deviceselectrically connected in parallel, for increased capacity withoutincreasing the overall lateral footprint of the thin film-based energystorage device.

FIG. 9 illustrates a side view of a thin film-based energy storagedevice having laterally adjacent current collectors and electrodelayers, where the current collector layers and the electrode layers areformed on opposing surfaces of a perforated substrate, for increasedcapacity without increasing the overall lateral footprint of the thinfilm-based energy storage device.

FIG. 10A illustrates a plan view of an electrode arrangement of a thinfilm-based energy storage device having laterally adjacent currentcollectors and electrode layers, where the first and second electrodesare rectangular in shape and have widths that overlap in a lateraldirection.

FIG. 10B illustrates a plan view of an electrode arrangement of a thinfilm-based energy storage device having laterally adjacent currentcollectors and electrode layers, where the first and second electrodesare rectangular in shape and have lengths that overlap in a lateraldirection.

FIG. 10C illustrates a plan view of an electrode arrangement of a thinfilm-based energy storage device having laterally adjacent currentcollectors and electrode layers, where each of the first and secondelectrodes has a plurality of regularly spaced rectangular protrusionsor fingers, where the rectangular protrusions or fingers of the firstand second electrodes are interlaced or interleaved such that theyalternate in a lateral direction, for increased overlapping edge lengthsof the first and second electrodes.

FIG. 10D illustrates a plan view of an electrode arrangement of a thinfilm-based energy storage device having laterally adjacent currentcollectors and electrode layers, where each of the first and secondelectrodes has a plurality of regularly spaced rounded protrusions orfingers, where the rounded protrusions or fingers of the first andsecond electrodes are interlaced or interleaved such that they alternatein a lateral direction, for increased overlapping edge lengths of thefirst and second electrodes.

FIG. 10E illustrates a plan view of an electrode arrangement of a thinfilm-based energy storage device having laterally adjacent currentcollectors and electrode layers, where each of the first and secondelectrodes has a plurality of regularly spaced elongated protrusions orfingers, where the elongated protrusions or fingers of the first andsecond electrodes are interlaced or interleaved such that they alternatein a lateral direction, for increased overlapping edge lengths of thefirst and second electrodes.

FIG. 11A illustrates a plan view of an electrode arrangement of a thinfilm-based energy storage device having laterally adjacent currentcollectors and electrode layers, similar to the arrangement illustratedin FIG. 10E, where the first and second electrodes have about the samesurface area.

FIG. 11B illustrates a plan view of an electrode arrangement of a thinfilm-based energy storage device having laterally adjacent currentcollectors and electrode layers, similar to the arrangement illustratedin FIG. 10E, where the first and second electrodes have differentsurface areas, where the ratio of surface areas between the first andsecond electrode layers is adjusted in accordance with a molar ratio ofthe active materials.

FIG. 12A illustrates a plan view of an intermediate structure at a stagein fabrication of thin film-based energy storage device having laterallyadjacent current collectors and electrode layers, similar to thearrangement illustrated in FIG. 10E, after depositing first and secondcurrent collectors.

FIG. 12B illustrates a plan view of an intermediate structure at afurther stage in fabrication of the energy storage device, afterdepositing a first electrode layer over the first current collectorillustrated in the intermediate structure illustrated in FIG. 12A.

FIG. 12C illustrates a plan view of an intermediate structure at afurther stage in fabrication of the energy storage device, afterdepositing a second electrode layer over the second current collectorillustrated in the intermediate structure illustrated in FIG. 12B.

FIG. 12D illustrates a plan view of an intermediate structure at afurther stage in fabrication of the energy storage device, afterdepositing a separator over the first and second electrode layersillustrated in the intermediate structure illustrated in FIG. 12C.

FIG. 13 illustrates a cross-sectional view of a thin film-based energystorage device having laterally adjacent current collectors andelectrode layers, similar to the arrangement illustrated in FIG. 10E,that is fabricated according to the fabrication process illustrated inFIGS. 12A-12D.

FIG. 14A illustrates a plan view of an intermediate structure at a stagein fabrication of a thin film-based energy storage device havinglaterally adjacent current collectors and electrode layers that haveoverlapping portions in the vertical direction, after depositing firstand second current collectors each having a plurality of regularlyspaced elongated protrusions or fingers, where the elongated protrusionsor fingers are interlaced or interleaved such that they alternate in alateral direction.

FIG. 14B illustrates a plan view of an intermediate structure at afurther stage in fabrication of the energy storage device, afterdepositing a first electrode layer over the first current collectorillustrated in the intermediate structure illustrated in FIG. 14A.

FIG. 14C illustrates a plan view of an intermediate structure at afurther stage in fabrication of the energy storage device, afterdepositing a separator over the first electrode layer illustrated in theintermediate structure illustrated in FIG. 14C.

FIG. 14D illustrates a plan view of an intermediate structure at afurther stage in fabrication of the energy storage device, afterdepositing a second electrode layer over the separator and over thesecond current collector illustrated in the intermediate structureillustrated in FIG. 14C.

FIG. 15 illustrates a cross-sectional view of a thin film-based energystorage device having laterally adjacent current collectors andelectrode layers that have overlapping portions in the verticaldirection, that is fabricated according to the fabrication processillustrated in FIGS. 14A-14D.

FIG. 16 illustrates plan views of intermediate structures at variousstages of fabrication of a thin film-based energy storage device havinglaterally adjacent current collectors and electrode layers, where theenergy storage device includes three units or cells that are connectedin electrical series. The stages of fabrication include four impressionsthat form three layer levels.

FIG. 17 illustrates a side view of a thin film-based energy storagedevice having laterally adjacent current collectors and electrodelayers, where the energy storage device is fabricated according to thefabrication process illustrated in FIG. 16, and includes four units orcells that are connected in electrical series.

FIG. 18 illustrates plan views of intermediate structures at variousstages of fabrication of thin film-based energy storage device havinglaterally adjacent current collectors and electrode layers that haveoverlapping portions in the vertical direction, where the energy storagedevice includes three units or cells that are connected in electricalseries. The stages of fabrication include four impressions that formthree layer levels.

FIG. 19 illustrates a side view a thin film-based energy storage devicehaving laterally adjacent current collectors and electrode layers thathave overlapping portions in the vertical direction, where the energystorage device is fabricated according to the fabrication processillustrated in FIG. 18, and includes three units or cells that areconnected in electrical series.

FIG. 20 illustrates plan views of intermediate structures at variousstages of fabrication of a thin film-based energy storage device havinglaterally adjacent current collectors and electrode layers, where eachof the first and second electrodes has a plurality of regularly spacedrectangular protrusions or fingers, where the rectangular protrusions orfingers of the first and second electrodes are interlaced or interleavedsuch that they alternate in a lateral direction. The energy storagedevice includes two units or cells that are connected in electricalseries and is fabricated in four impressions that form three layerlevels.

FIG. 21 illustrates plan views and corresponding cross-sectional viewsof intermediate structures at various stages of fabrication of a thinfilm-based energy storage device having laterally adjacent currentcollectors and electrode layers, where each of the first and secondelectrodes are configured as a plurality of concentric rings. The energystorage device includes two units or cells that are connected inelectrical series and is fabricated in four impressions that form threelayer levels.

FIG. 22 illustrates plan views of intermediate structures at variousstages of fabrication of a thin film-based energy storage device havinglaterally adjacent current collectors and electrode layers, where eachof the first and second electrodes are configured as a plurality ofconcentric rings having a plurality of regularly spaced elongatedprotrusions or fingers, where the elongated protrusions or fingers ofthe first and second electrodes are interlaced or interleaved such thatthey alternate in a circular direction, for increased overlapping edgelengths of the first and second electrodes. The energy storage deviceincludes two units or cells that are connected in electrical series andis fabricated in four impressions that form three layer levels.

FIG. 23 illustrates a plan view of a wearable thin film-based electronicdevice that is integrated with a thin film-based energy storage device,where the energy storage device has a plurality of units or cells thatare connected in electrical series.

FIG. 24 illustrates a plan view of a field-configurable thin film-basedenergy storage device having an array of units or cells that are formedon a substrate having perforations such that a desired number of unitsor cells can be connected in electrical series or parallel forcustomizable voltage and capacity.

FIG. 25 illustrates a side view of an integrated thin film-basedelectronic device having integrated therein a thin film-based energystorage device having laterally adjacent current collectors andelectrode layers, and a thin film-based core device having laterallyarranged electrical terminals and powered by the thin film-based energystorage device.

FIG. 26 illustrates a side view of an integrated thin film-basedelectronic device having integrated therein a thin film-based energystorage device having laterally adjacent current collectors andelectrode layers, and a thin film-based core device having verticallyarranged electrical terminals and powered by the thin film-based energystorage device.

FIG. 27 illustrates a side view of an integrated thin film-basedelectronic device having integrated therein a thin film-based energystorage device having vertically stacked current collectors andelectrode layers, and a thin film-based core device having verticallyarranged electrical terminals and powered by the thin film-based energystorage device.

FIG. 28 illustrates a thin film-based light-emitting device havingvertically arranged electrical terminals and configured to be integratedwith and powered by various thin film-based energy storage devicesdescribed herein.

FIG. 29 illustrates a side view of an integrated thin film-basedelectronic device having integrated therein a thin film-based energystorage device having laterally adjacent current collectors andelectrode layers, and the thin film-based light-emitting deviceillustrated with respect to FIG. 28 having vertically arrangedelectrical terminals and powered by the thin film-based energy storagedevice.

FIG. 30 illustrates a top down view of an integrated thin film-basedelectronic device having integrated therein a thin film-based energystorage device including a plurality of units or cells that areconnected in electrical series, and a thin film-based light-emittingdevice illustrated with respect to FIG. 28 having vertically arrangedelectrical terminals and powered by the thin film-based energy storagedevice.

FIG. 31 illustrates a top down optical image of an integrated thinfilm-based electronic device having integrated therein a thin film-basedenergy storage device including a plurality of units or cells that areconnected in electrical series, where each of the electrodes of eachunit or cell have a plurality of regularly spaced elongated protrusionsor fingers, and a thin film-based light-emitting device illustrated withrespect to FIG. 28 having vertically arranged electrical terminals andpowered by the thin film-based energy storage device.

FIG. 32 illustrates a side view of an integrated thin film-basedelectronic device having integrated therein a thin film-based energystorage device having laterally adjacent current collectors andelectrode layers, and a thin film-based energy harvesting deviceconfigured to charge/recharge the thin film-based energy storage device,in a charging mode.

FIG. 33 illustrates a side view of an integrated thin film-basedelectronic device having integrated therein a thin film-based energystorage device having laterally adjacent current collectors andelectrode layers, and a thin film-based energy harvesting deviceconfigured to charge/recharge the thin film-based energy storage device,in a discharging mode.

FIG. 34 illustrates a side view of an integrated thin film-basedelectronic device having integrated therein a thin film-based energystorage device having laterally adjacent current collectors andelectrode layers, and a thin film-based energy harvesting deviceconfigured to charge/recharge the thin film-based energy storage device.

FIG. 35 illustrates a manufacturing kit of a thin film-based energystorage device, which includes a thin film-based energy storage devicehaving laterally adjacent current collectors and electrode layers and adry separator, and a separately provided electrolyte configured to wetthe dry separator prior to use.

DETAILED DESCRIPTION

Although certain embodiments and examples are described below, those ofskill in the art will appreciate that the invention extends beyond thespecifically disclosed embodiments and/or uses and obvious modificationsand equivalents thereof. Thus, it is intended that the scope of theinvention herein disclosed should not be limited by any particularembodiments described below.

As described herein, printing or additive manufacturing refers to aprocess in which materials are accumulated, grown or increased in massin a layer-by-layer fashion to to form a two- or three-dimensionalobject. The added materials can include liquid and/or solid. The objectcan be added or joined with an existing component, such as a substrate.

Generally, advantages of manufacturing electronic devices by printingover other techniques include compatibility with forming complex shapes,improved form factor, reduced overall thickness, reduced devicefootprint, ease of integration with other devices, e.g., thin film-baseddevices, flexibility, reduction in cost, forming large area structures,mass manufacturing, lower material cost and ability to combine withother high throughput manufacturing processes such as roll-to-rollmanufacturing, to name a few,

As described herein, a printed device refers to a device having at leastone layer or feature that is printed using a printing process, havingmultiple features or layers printed using a printing process, or havingall features or layers printed using a printing process.

In various embodiments described herein, one or more components ofvarious devices and apparatuses described advantageously may comprisethin film features. One or more of the thin film features may be printedfeatures. As described herein, suitable printing processes for formingthe thin features include gravure printing, screen printing,lithography, flexography, ink-jet printing, rotary screen printing andstenciling, among other suitable printing processes. One or more ofthese printing processes may be combined with other high volumemanufacturing techniques, e.g., roll-to-roll processing. Printing partsof devices or components thereof can provide various advantages,including reduced thickness, compact dimensions and low waste, to name afew. Printed devices can also enable increased functionalities for agiven footprint of the device by enabling, among other things, stackingof the printed devices or components thereof. Unlike devicesmanufactured using other processes, some printed devices can also beflexible, which can be suitable for wearable devices including wearablemedical devices, displays, sensors, smartcards, smart packaging, smartclothing, signage, advertisements, among other devices.

According to various embodiments, a thin film-based energy storagedevice (ESD) comprises electrically separated current collector layersformed on a substrate. The current collector layers include a firstcurrent collector layer of a first type, which may be a currentcollector configured as one of an anode or a cathode of the ESD, and asecond current collector layer of a second type, which may be a currentcollector configured as the other one of the anode or the cathode of theESD. The first and second current collector layers may be deposited,e.g., printed, over or on a common surface of the substrate. The ESDadditionally comprises a first electrode layer of a first type, e.g., alayer of one of an anode or a cathode, that is formed over or on, e.g.,printed on, the first current collector layer of the first type. The ESDadditionally comprises a second electrode layer of a second type, e.g.,a layer of the other of the anode or the cathode, that is formed over oron, e.g., printed on, the second current collector layer of the secondtype. The ESD further comprises a separator, e.g., a printed separator,that may be formed over or on to contact one or both of the firstelectrode layer and the second electrode layer.

As described herein, a thin film-based ESD may include one or more of aprimary battery, a secondary battery, a supercapacitor and abattery-supercapacitor hybrid device. When the ESD includes a primarybattery, the ESD can be configured as a zinc/carbon,zinc/alkaline/manganese, magnesium/manganese dioxide, zinc/mercuricoxide, cadmium/mercuric oxide, zinc/silver oxide, zinc/air,lithium/soluble cathode and lithium/solid cathode primary battery, toname a few. When the ESD includes a secondary battery, the ESD can beconfigured as a nickel/iron, silver/iron, iron/air, nickel/cadmium,nickel/metal hydride, nickel/zinc, zinc/silver oxide, lithium-ion,lithium/metal, Zn/MnO₂, zinc/air, aluminum/air, magnesium/air, andlithium/air/lithium/polymer secondary batteries, to name a few.

In some embodiments, a thin film-based ESD may comprise a supercapacitorin which both electrodes are configured as a double-layer capacitor,both electrodes are configured as a pseudo capacitor, or one electrodeis configured as a double-layer while the other electrode is configuredas a pseudo capacitor. In some implementations, the thin film-based ESDmay comprise a supercapacitor having symmetric printed electrodes, whereeach of the electrodes comprises, e.g., zinc oxide (Zn_(x)O_(y)) ormanganese oxide (Mn_(x)O_(y)). In other implementations, the thinfilm-based ESD may comprise a supercapacitor having symmetric printedelectrodes, where each of the electrodes has formed thereon carbonnanotubes. In some implementations, the thin film-based ESD may comprisea supercapacitor having asymmetric printed electrodes, where one of theelectrodes comprise, e.g., zinc oxide (Zn_(x)O_(y)) or manganese oxide(Mn_(x)O_(y)), while the other of the electrodes comprise carbonnanotubes.

As described herein, supercapacitors, sometimes also referred to asultracapacitors, electric double layer capacitors (EDLC) orelectrochemical capacitors, are relatively new energy storage deviceswhose characteristics are advantageously similar to traditionalelectrostatic capacitors in some aspects while being similar totraditional batteries, e.g., secondary batteries, in some other aspects.

Similar to certain batteries, supercapacitors have a cathode or apositive electrode and an anode or a negative electrode that areseparated by a porous separator and an electrolyte. For example, theseparator may comprise a dielectric material permeable to ions andsoaked in the electrolyte. Ion transport which occurs from one electrodeto the other as part of an electrochemical reaction during charge ordischarge of a battery does not occur in supercapacitors.

While supercapacitors are similar to traditional electrostaticcapacitors in some aspects, e.g., relatively fast charging capability,they have much higher capacitance compared to traditional electrostaticcapacitors. Unlike traditional electrostatic capacitors that storeenergy in electrodes separated by a dielectric, supercapacitors storeenergy at one or both of interfaces between a cathode and an electrolyteand an anode and the electrolyte.

Capacitance values of supercapacitors may be much higher thantraditional electrostatic capacitors. Some supercapacitors have lowervoltage limits compared to traditional electrostatic capacitors. Forexample, some supercapacitors are operationally limited to about 2.5-2.8V. Some supercapacitors may operate at voltages of 2.8 V and higher.Certain such supercapacitors may exhibit a reduced service life.

Supercapacitors generally have much higher power density than batteriesbecause they can transport charge much faster than batteries.Supercapacitors generally have much lower internal resistance comparedto batteries and, as a result, they do not generate as much heat duringquick charge/discharge. Some supercapacitors can be charged anddischarged millions of times, while many secondary batteries can havesignificantly shorter typical life cycle of 500-10000 times. Somesupercapacitors have significantly lower energy density compared tobatteries. Some commercial supercapacitors are more expensive (highercost per Watt) than commercial batteries.

Because of these and other characteristics, supercapacitors are used inapplications in which many rapid charge/discharge cycles may be neededrather than long term energy storage. For example, applications oflarger units of supercapacitors include cars, buses, trains, cranes andelevators, to name a few, where they are used for regenerative braking,short-term energy storage or burst-mode power delivery. Applications ofsmaller units of supercapacitors include memory backup for staticrandom-access memory (SRAM). Other current or future applications ofsupercapacitors include various consumer electronics, including mobilephones, laptops, electric cars and various other devices in whichbatteries are used. Because they can be recharged much faster comparedto batteries, they are especially attractive for devices that canbenefit from faster charge rates, e.g., minutes instead of hours thatcurrent electric vehicles or mobile phones may spend charging.

In some devices, supercapacitors are used in conjunction with batteriesto take advantage of advantageous characteristics of both. In theseapplications, supercapacitors are used when a quick charge is needed tofill a short-term power need, whereas batteries are used to providelong-term energy. Combining the two into a hybrid energy storage devicecan satisfy both needs while reducing battery stress, which may in turnenable a longer service life of the battery and the supercapacitor.

Without being bound to any theory, supercapacitors can store energy bydifferent mechanisms, which include electric double-layer capacitanceand/or pseudocapacitance. Double layer capacitance has electrostaticcharacteristics, while pseudocapacitance has electrochemicalcharacteristics. The different mechanisms are described in more detailbelow. Depending on whether the storage mechanism has double-layercapacitance characteristics and/or pseudocapacitance characteristics,and depending on whether the supercapacitor has two same or symmetricelectrodes or two different or asymmetric electrodes, supercapacitorscan be configured as one of three distinct groups of supercapacitorsaccording to some embodiments.

A first group of supercapacitors has both electrodes configured aspseudo capacitors, where each of the electrodes comprises a transitionmetal oxide (e.g., manganese oxide or zinc oxide) and is configured togive rise to pseudo capacitance. For example, the metal oxide may be inthe form of nanostructures. A second group of supercapacitors has bothelectrodes configured as EDLCs, where each of the electrodes comprisescarbon (e.g., carbon nanotubes) and is configured to give rise to doublelayer capacitance. For example, the carbon may be formed asnanostructures. A third group of supercapacitors, which may be referredto as hybrid supercapacitors, has one of the electrodes that isconfigured as a EDLC and the other of the electrodes that is configureda pseudo capacitor. When included as part of a hybrid capacitor, theelectrode configured as the pseudo capacitor may serve as a cathode or apositively charged electrode, and the electrode configured as the EDLCmay serve as an anode or a negatively charged electrode.

The ESDs fabricated according to various embodiments offer manyadvantages. For example, some performance metrics of a thin film-basedESD can be dependent on the thicknesses of various layers of the ESD.The thicknesses of various layers of the ESD can in turn be limited bythe deposition technique employed to form the layers. For example, thecapacity of some thin film-based ESDs can be limited by thicknesses ofthe electrode layers that contain the electrode active materials. Due tocracking and/or delaminating of the layers, which may result from filmstress and/or interfacial energy, the capacity of the ESD may be limitedby the thicknesses of the electrode layers that can be reliablydeposited. By printing, relatively thicker layers of one or more layersof the ESDs may be achieved. For example, as described by variousexamples described herein, electrically connected printed layers can beformed on multiple surfaces of a feature and stacked on top of oneanother. Thus, by employing various structural features and fabricationmethods including printing methods described herein, thin film-basedESDs according to embodiments disclosed herein can have higher capacity,among other advantages.

As used herein, an electrode active material refers to a component of anelectrode that is chemically associated with the energy storagemechanism. For example, in batteries, an electrode active material is acomponent of a cathode or an anode that participates in anelectrochemical charge or discharge reaction. In supercapacitors, anelectrode active material is a component of a cathode or an anode thatparticipates in electrostatic double layer capacitance (EDLC) orelectrochemical pseudocapacitance.

Printing one or more layers of the thin film-based ESD may enablecustomization of the operational current and/or resistance of the ESD.For example, in part because printing allows for higher levels ofcustomization of the shape and thickness of the individual layers, thesurface areas of the electrodes that may be available forelectrochemical reactions of the ESD device may be customized moreeasily. Printing one or more layers of the thin film-based ESD allowsmultiple units of ESDs or cells to be electrically connected in seriesand/or in parallel, to customize the voltage and/or capacity of the ESD.

Printing one or more layers of the thin film-based ESD may furtherenable reduction in the overall thickness and/or footprint of variousthin film-based devices integrating the thin film-based ESD. This is inpart because printing allows for higher levels of customization of theshape and thicknesses of the individual layers.

Printing one or more layers of the thin film-based ESD may furtherenable reduction in the overall number of process steps. For example,one or more masking steps that may be employed in subtractive patterningtechniques may be omitted by printing one or more layers. In addition,by printing different layers laterally and/or simultaneously, the numberof overall processing steps can be reduced.

Printing one or more layers of the thin film-based ESD may furtherenable higher levels of integration with the thin film-based electronicdevices powered by the ESD. This may be because similar materials may beused to print different components of the ESD and the electronic devicepowered by the ESD. Some layers of the ESD and the electronic device mayeven be printed simultaneously.

As described herein, in various embodiments, some of the layers of theESD are printed, while in other embodiments, all layers of the ESD areprinted. The layers that are not printed may be deposited by a suitablemethod, including plating, evaporation, sputtering, chemical vapordeposition or any other thin film deposition techniques.

Vertically Stacked Versus Laterally Adjacent Electrode Configurations inThin Film-Based Energy Storage Devices

Generally, thin film-based energy storage devices (ESDs), e.g., printedESDs, may be categorized based on the relative orientations of thecurrent collectors and/or the electrode layers. The first category ofESDs includes thin film-based energy storage devices having verticallystacked current collectors and electrode layers, and the second categoryof ESDs includes thin film-based energy storage devices having laterallyadjacent current collectors and electrode layers. Both categories ofESDs can be fully printed on a substrate and provide various advantagesdescribed above, compared to ESDs in which the current collectors and/orelectrodes are formed separately, e.g., on different substrates, andsubsequently integrated by adjoining them with a separator disposedtherebetween. The ESDs according to various embodiments described hereinhaving laterally adjacent current collectors on the same side of thesubstrate are advantageous for integrating with other devices on thesame substrate, at least because the electrical connections can easilybe made, e.g., by printing the current collectors that extend into orcontact conductive leads of the integrated device.

FIG. 1 illustrates an example of a thin film-based energy storage device(ESD) 100 having vertically stacked current collectors and electrodelayers. The ESD 100 includes a substrate 104 on which a stack of layersis formed. The stack of layers includes a first current collector 108 ofa first type formed over or on the substrate 104, a first electrodelayer 112 of a first type formed over or on the first current collector108, a separator 116 formed over or on the first electrode layer 112, asecond electrode layer 120 of a second type formed over or on theseparator 116 and a second current collector 124 of a second type formedover or on the second electrode layer 120. The ESD 100 may be fabricatedin five printing impressions or processes, including sequentiallyprinting the first current collector 108, the first electrode layer 112,the separator 116, the second electrode layer 120 and the second currentcollector 124.

The first electrode layer 112 has lateral dimensions that are the sameor smaller than those of the first current collector 108 such that thefirst electrode layer 112 if formed laterally within the lateralfootprint of the first current collector 108. The separator 116 isformed on the first electrode layer 112 to electrically separate thefirst current collector 108 and the first electrode layer 112 from thesecond electrode layer 120 and the second current collector 124. In theillustrated embodiment the separator 116 contacts the first currentcollector 108 on a first side, extends to encapsulate the firstelectrode layer 112, and extends on a second side to cover a sidesurface of the first current collector 108 and to contact the substrate104. The second electrode layer 120 has lateral dimensions that are thesame or smaller than those of the separator 116 such that the secondelectrode layer 120 extends laterally within the lateral footprint ofthe separator. The second current collector 124 covers the secondelectrode layer and extends vertically to cover side surfaces of thesecond electrode layer 120 and the separator 116 and to contact thesubstrate 104.

While not shown for clarity, in various embodiments disclosed herein,the first current collector 108 may be electrically connected to furtherconductive structures, e.g., printed circuit patterns or a firstelectrical terminal of an electronic device to be powered by the ESD100, and the second current collector 124 may be electrically connectedto further conductive structures, e.g., printed circuit patterns or asecond electrical terminal of the device to be powered by the ESD 100.In addition, while not shown for clarity, in various embodimentsdisclosed herein, thus formed ESD may be covered or encapsulated byprotective or passivating layers or structures.

Still referring to FIG. 1, in operation, when a voltage is appliedbetween the first current collector 108 and the second current collector124, ions may be exchanged between the first electrode layer 112 and thesecond electrode layer 120 through the separator 116, thereby chargingor discharging the ESD 100. Advantageously, a substantial or apredominant portion of the ionic exchange may occur in a verticaldirection between overlapping portions of the first electrode layer 112and the second electrode layer 120. Thus, a larger area of overlapbetween the first electrode layer 112 and the second electrode layer 120can lead to higher current during charge/discharge, lower resistance,higher power and/or shorter time to charge.

As described herein, a current collector of a first type refers to oneof a positive or a negative current collector, and a current collectorof a second type refers to the other of the positive or the negativecurrent collector. Similarly, an electrode of a first type refers to oneof a positive or a negative electrode, or one of a cathode or an anode,and an electrode of a second type refers to the other of the positive orthe negative electrode, or the other of the cathode or the anode. Asdescribed herein, the positive current collector and the electrodecorrespond to a cathode and the negative current collector and theelectrode correspond to an anode. Thus, in FIG. 1, the first currentcollector 108 and the first electrode layer 112 may be one of a positiveor negative current collector and one of a positive or negativeelectrode, respectively, and the second current collector 124 and thesecond electrode 120 may be the other of the positive or negativecurrent collector and one of the positive or negative electrode,respectively.

FIG. 2A illustrates a side view of an example of a thin film-based ESD200 having laterally adjacent current collectors and electrode layers,according to embodiments. FIG. 2B illustrates a plan view of electrodelayers of the printed energy storage device illustrated in FIG. 2A.Similar to the ESD 100 illustrated with respect to FIG. 1, the ESD 200includes a substrate 104, a first current collector 108, a secondcurrent collector 124, a first electrode layer 112, a second electrodelayer 120 and a separator 116. Unlike the ESD 100 illustrated in FIG. 1,in the ESD 200, the first and second current collectors 108, 124 areformed laterally adjacent to each other over or on the substrate 104 andare separated by a gap 210 in a lateral direction, instead of beingvertically separated as in the ESD 100 described above with respect toFIG. 1. The first electrode layer 112 is formed over or on the firstcurrent collector 108 and the second electrode layer 120 is formed overor on the second current collector 124. Thus, the first electrode layer112 and the second electrode layer 120 are also disposed laterallyadjacent to each other and separated by the gap 210 in the lateraldirection, instead of being vertically separated. The separator 120 isformed over or on to electrically separate the first and secondelectrode layers 112, 120.

The first electrode layer 112 has lateral dimensions that are about thesame or smaller than those of the first current collector 108 such thatthe first electrode layer 112 is formed laterally within the footprintof the first current collector 108. Similarly, the second electrodelayer 120 has lateral dimensions that are about the same or smaller thanthose of the second current collector 124 such that the second electrodelayer 120 is formed laterally within the footprint of the second currentcollector 124. The separator 116 is formed over or on, e.g., contacts, afirst side surface and a second side surface of the first currentcollector 108 and encapsulates the first electrode 112, and is formedover or on, e.g., contacts, a first side surface and a second sidesurface of the second current collector 124 and encapsulates the secondelectrode layer 120. The separator 116 fills the gap 210 formed betweenthe first and second electrode layers 112, 120, thereby electricallyseparating the side surfaces of the first and second electrode layers112, 120 facing each other in the lateral direction. The separator 116also fills the portion the gap 210 formed between the first and secondcurrent collectors 108, 124, thereby electrically separating the sidesurfaces of the first and second current collectors 108, 124 facing eachother.

Still referring to FIGS. 2A and 2B, in operation, when a voltage isapplied between the first current collector 108 and the second currentcollector 124, ions may be exchanged between the first electrode layer112 and the second electrode layer 120 through the separator 116,thereby charging or discharging the ESD 200. Unlike the ESD 100 (FIG.1), because of the lateral arrangement of the first and second electrodelayers 112, 120, a substantial or a predominant portion of the ionicexchange may occur in a lateral direction. The ionic exchange can occurbetween side surfaces and top surfaces of the first and second electrodelayers 112, 120. The relative amounts of ionic current between the sidesurfaces and the top surfaces can vary depending on the thickness of thelayers (and the area of overlap between the side surfaces) and the areasof the top surfaces. When the area of overlap between the side surfacesis relatively large, e.g., a substantial or a predominant portion of theionic exchange may occur between overlapping portions of the sidesurfaces of the first electrode layer 112 and the second electrode layer120 facing each other across the gap 210.

When one or more layers of the ESD 200 are printed, the method offabricating the ESD 200 includes depositing, e.g., printing, the firstcurrent collector 108 and the second current collector 124 that arelaterally adjacent and electrically separated over or on a commonsubstrate 104. The first and second current collector layers 108 and 124can be printed, simultaneously, and can be formed of the same material.After printing the first and second current collectors 108, 124, thefirst electrode layer 112 and the second electrode layer 120 aredeposited, e.g., printed, over or on the respective current collectors108 and 124, respectively. After printing the first and secondelectrodes 112, 120, the separator 116 is deposited, e.g., printed, overor on the first and second electrode layers 112, 120. When the first andsecond current collector layers 108, 124 are simultaneously printed, theillustrated ESD 200 may be fabricated in four deposition steps orprinting impressions, including simultaneously printing the first andsecond current collectors 108, 124, printing the first electrode layer112, printing the second electrode layer 124 and printing the separator116.

Thus, compared to the method of fabricating the ESD 100 havingvertically stacked electrodes as illustrated in FIG. 1, the ESD 200having laterally disposed electrodes can advantageously be fabricated,e.g., printed, in fewer process steps, e.g., in as few as four processsteps or printing impressions, compared to five process steps orprinting impressions used in fabricating the ESD 100 illustrated in FIG.1.

The thicknesses of the current collectors can vary depending on theapplication. For example, in some implementations, it may be desirableto have thicker first and second current collectors 108, 124 for lowerelectrical resistance. In some implementations, it may be desirable tohave thicker first and second electrode layers 112, 120 to providehigher capacity. In ESD 200, thicker electrode layers 112, 120 may alsoprovide higher current capability.

In various embodiments described herein, each of the individual layersor the entire ESD can have a thickness in a range of 1-10 microns, 10-50microns, 50-100 microns, 100-200 microns, 200-300 microns, 300-400microns, 400-500 microns, 500-600 microns, 600-700 microns, 700-800microns 800-900 microns, 900-1000 microns, 1000-1200 microns, 1200-1400microns, 1400-1600 microns, 1600-1800 microns, 1800-2000 microns, or athickness in a range defined by any of these values.

It will be appreciated that vertical electrode arrangements (e.g., ESD100 in FIG. 1) and lateral electrode arrangements (e.g., ESD 200 inFIGS. 2A-2B) offer same or different advantages. As discussed above, theESD 200 (FIGS. 2A-2B) can be fabricated with relatively fewer processsteps and can be thinner compared to the ESD 100 (FIG. 1). On the otherhand, ESD 100 (FIG. 1) can have a smaller lateral footprint compared tothe ESD 200 (FIGS. 2A-2B) for the same capacity and current. Compared tothe ESD 100 (FIG. 1), the ESD 200 may advantageously be permitted tohave a lower overall device thickness and/or relatively thickerindividual layers for similar overall thickness, because the loweroverall number of vertically stacked layers may reduce the risk ofcracking and/or delamination at the interfaces. On the other hand, theESD 200 (FIGS. 2A-2B) may have relatively lower current capabilitycompared to the ESD 100 (FIG. 1) because of relatively smaller overlapbetween electrodes. In the following, various other embodiments andtheir components that aim to optimize the advantages offered by the twodifferent types of ESDs illustrated with respect to FIG. 1 and FIGS.2A/2B are described. Compared to the ESD 100 (FIG. 1), the secondcurrent collector 124 of the ESD 200 (FIG. 2) does not have relativelylong vertical portion extending from the substrate 104, which can reducethe overall resistance of the ESD 200. In addition, when the verticalheight of the ESD 100 is relatively high, a mechanical support layer(not shown in FIG. 1) may be provided to support the vertical portion ofthe second current collector 124 of the ESD 100, which is advantageouslynot needed in the ESD 200.

Printing Methods for Fabricating Thin Film-Based Energy Storage Devices

One or more layers of the ESDs disclosed herein can be printed from anink containing the component materials. The one or more layers or theentire ESD device can be printed using a suitable printing technique.Example printing processes that can be used to print the one or morelayers include coating, rolling, spraying, layering, spin coating,lamination and/or affixing processes, for example, screen printing,inkjet printing, electro-optical printing, electroink printing,photoresist and other resist printing, thermal printing, laser jetprinting, magnetic printing, pad printing, flexographic printing, hybridoffset lithography, gravure and other intaglio printing, die slotdeposition, among other suitable printing techniques.

The inks for printing one or more layers of the ESDs disclosed hereincan be prepared by combining various ink components, including variousactive materials associated with the electrochemical reaction of theESDs with a suitable solvent and/or a binder, and mixing using asuitable techniques such as mixing using a stir bar, mixing with amagnetic stirrer, vortexing (using a vortex machine), shaking (using ashaker), planetary centrifugal mixing, by rotation, three roll milling,ball milling, sonication and mixing using mortar and pestle, to name afew.

After printing the one or more layers using an ink, the one or morelayers can be treated using one or more post-printing processes,including drying/curing processes including short wave infrared (IR)radiation, medium wave IR-radiation, hot air conventional ovens,electron beam curing ultraviolet (UV) curing and near infraredradiation, among other techniques.

Compositions and Materials of Layers of Thin Film-Based Energy StorageDevices

In the following, compositions, materials and structures of variouslayers of thin film ESDs according to embodiments are described.

The thin film-based ESDs comprise various layers formed, e.g., printed,on a substrate 104. The substrate may be formed of a suitable material,which may have attributes such as being flexible or rigid, thermallyconductive or insulating, optically transparent or opaque, or organic orinorganic, among other attributes. When the first and second currentcollectors 108, 124 are directly formed thereon, the substrate 104 isformed of a sufficiently electrically insulating material such that thefirst and second current collectors 108, 124 are not electricallyshorted or the leakage current therebetween is sufficiently low. Asdescribed herein, an electrically insulating material refer to amaterial having negligible electronic carriers such as electrons andholes that may be generated thermally, electrically or optically underordinary operational conditions, and exclude semiconductor materialssuch as silicon. However, the substrate 104 may include an electricallyconductive or semiconducting material, whose surface region has beenrendered sufficiently electrically insulating, e.g., by forming aninsulating layer or a coating on a semiconducting or conductivesubstrate prior to forming the first and second current collectors 108,124, such that they are not electrically shorted.

Suitable classes of materials that can be included as part of thesubstrate 104 include, but not limited to, a polymeric material, atextile-based material, a device, a metallic material, a semiconductormaterial or a cellulose-based material. Specific examples of thesubstrate 104 include, e.g., a plastic (e.g., polyester, polyimide,polycarbonate), a dielectric (e.g., a metal oxide, metal nitride, metalcarbide), a polyester film (e.g., Mylar), a polycarbonate film, asemiconductor (e.g., silicon), a conductor (e.g., an aluminum foil, acopper foil, a stainless steel foil), a carbon foam, or a paper (e.g., agraphite paper, a graphene paper, a cardboard, a coated paper, such as aplastic-coated paper, and/or a fiber paper), or combinations thereof,and/or the like.

According to various embodiments, the first electrode layer 112 may beone of a cathode or an anode and the second electrode layer 120 mayinclude the other of the cathode or the anode. The cathode of an energystorage device may include a cathode electrode active material, such asa silver-containing material or a manganese-containing material. Forexample, the cathode may include a silver(I) oxide (Ag₂O), asilver(I,III) oxide (AgO), a mixture comprising silver(I) oxide (Ag₂O)and manganese(IV) oxide (MnO₂), manganese (II, III) oxide (Mn₃O₄),manganese (II) oxide (MnO), manganese (III) oxide (Mn₂O₃), and/ormanganese oxyhydroxide (MnOOH), a mixture comprising silver(I) oxide(Ag₂O) and nickel oxyhydroxide (NiOOH), silver nickel oxide (AgNiO₂),combinations thereof, and/or the like. The anode of an energy storagedevice may include an anode electrode active material, such as, such aszinc, cadmium, iron, nickel, aluminum, metal hydrate, hydrogen,combinations thereof, and/or the like. In some embodiments, the anodecan include zinc powder.

In some embodiments, the thin film-based ESDs disclosed herein mayinclude, e.g., as part of one or more of the first electrode layer 112,the second electrode layer 120 or the separator 116, a non-aqueouselectrolyte. The non-aqueous electrolyte may in turn include an organicelectrolyte based on acetonitrile, propylene carbonate, ethylenecarbonate, diethyl carbonate, dimethyl carbonate, ethyl acetate,1,1,1,3,3,3-hexafluoropropan-2-ol, adiponitrile, 1,3-propylene sulfite,butylene carbonate, γ-butyrolactone, γ-valerolactone, propionitrile,glutaronitrile, adiponitrile, methoxyacetonitrile,3-methoxypropionitrile, N,N-dimethylformamide, N,N-dimethylacetamide,N-methylpyrrolidinone, N-methyloxazolidinone,N,N″-dimethylimidazolininone, nitromethane, nitroethane, sulfonate,3-methylsulfonate, dimethylsulfoxide, trimethyl phosphate, or a mixturethereof, among other organic electrolytes.

In some embodiments, the electrolyte may include an ionic liquid. Asdescribed herein, ionic liquids are organic molten salts which consistessentially of ions and are liquid at temperature below 100° C. An ionicliquid has a cation and anion. The ionic liquid according to embodimentscan include any combination from the list of cations and the list ofanions below.

The cation of the ionic liquid can include one or more of:butyltrimethylammonium, 1-ethyl-3-methylimidazolium,1-butyl-3-methylimidazolium, 1-methyl-3-propylimidazolium,1-hexyl-3-methylimidazolium, choline, ethylammonium,tributylmethylphosphonium, tributyl(tetradecyl)phosphonium,trihexyl(tetradecyl)phosphonium, 1-ethyl-2,3-methylimidazolium,1-butyl-1-methylpiperidinium, diethylmethylsulfonium,1-methyl-3-propylimidazolium, 1-ethyl-3-methylimidazolium,1-methyl-1-propylpiperidinium, 1-butyl-2-methylpyridinium,1-butyl-4-methylpyridinium, 1-butyl-1-methylpyrrolidinium,diethylmethylsulfonium, or a combination thereof.

The anion of the ionic liquid can include one or more of:tris(pentafluoroethyl)trifluorophosphate, trifluoromethanesulfonate,hexafluorophosphate, tetrafluoroborate, ethyl sulfate, dimethylphosphate, trifluoromethanesulfonate, methansulfonate, triflate,tricyanomethanide, dibutylphosphate, bis(trifluoromethylsulfonyl)imide,bis-2,4,4-(trimethylpentyl) phosphinate, iodides, chlorides, bromides,nitrates, or a combination thereof.

In some embodiments, the electrolyte may further include an electrolytesalt, which may be organic-based, acid-based, base-based orinorganic-based. For example, an organic salt that may be included aspart of the electrolyte includes one or more of: tetraethylammoniumtetrafluoroborate, tetraethylammonium difluoro(oxalate)borate,methylammonium tetrafluoroborate, triethylmethylammoniumtetrafluoroborate, tetrafluoroboric acid dimethyldi ethylammonium,triethylmethylammonium tetrafluoroborate, tetrapropylammoniumtetrafluoroborate, methyltributylammonium tetrafluoroborate,tetrabutylammonium tetrafluoroborate, tetrahexylammoniumtetrafluoroborate, tetramethylammonium tetrafluoroborate, tetraethylphosphonium tetrafluoroborate, tetrapropylphosphonium tetrafluoroborate,tetrabutylphosphonium, tetrafluoroborate or a combination thereof.

An acid-based electrolyte that may be included as part of theelectrolyte includes one or more of H₂SO₄, HCl, HNO₃, HClO₄, acombination thereof and the like.

A base-based electrolyte that may be included as part of the electrolyteincludes one or more of KOH, NaOH, LiOH, NH₄OH, a combination thereofand the like.

An inorganic-based salt that may be included as part of the electrolyteincludes one or more of LiCl, Li₂SO₄, LiClO₄, NaCl, Na₂SO₄, NaNO₃, KCl,K₂SO₄, KNO₃, Ca(NO₃)₂, MgSO₄, ZnCl₂, Zn(BF₄)₂, ZnNO₃, a combinationthereof and the like.

Embodiments are not limited to organic electrolytes or ionic liquids. Inother embodiments, the ESDs according to embodiments includes an aqueouselectrolytes based on water.

In some embodiments, a low viscosity additive may be added to theelectrolyte. The low viscosity additive that may be included as part ofthe electrolyte includes one or more of water, alcohols such asmethanol, ethanol, N-propanol (including 1-propanol, 2-propanol(isopropanol or IPA), 1-methoxy-2-propanol), butanol (including1-butanol, 2-butanol (isobutanol)), pentanol (including 1-pentanol,2-pentanol, 3-pentanol), hexanol (including 1-hexanol, 2-hexanol,3-hexanol), octanol, N-octanol (including 1-octanol, 2-octanol,3-octanol), tetrahydrofurfuryl alcohol (THFA), cyclohexanol,cyclopentanol, terpineol; lactones such as butyl lactone; ethers such asmethyl ethyl ether, diethyl ether, ethyl propyl ether, and polyethers;ketones, including diketones and cyclic ketones, such as cyclohexanone,cyclopentanone, cycloheptanone, cyclooctanone, acetone, benzophenone,acetylacetone, acetophenone, cyclopropanone, isophorone, methyl ethylketone; esters such ethyl acetate, dimethyl adipate, proplyene glycolmonomethyl ether acetate, dimethyl glutarate, dimethyl succinate,glycerin acetate, carboxylates; carbonates such as propylene carbonate;polyols (or liquid polyols), glycerols and other polymeric polyols orglycols such as glycerin, diol, triol, tetraol, pentaol, ethyleneglycols, diethylene glycols, polyethylene glycols, propylene glycols,dipropylene glycols, glycol ethers, glycol ether acetates,1,4-butanediol, 1,2-butanediol, 2,3-butanediol, 1,3-propanediol,1,4-butanediol, 1,5-pentanediol, 1,8-octanediol, 1,2-propanediol,1,3-butanediol, 1,2-pentanediol, etohexadiol, p-menthane-3,8-diol,2-methyl-2,4-pentanediol; tetramethyl urea, n-methylpyrrolidone,acetonitrile, tetrahydrofuran (THF), dimethyl formamide (DMF), N-methylformamide (NMF), dimethyl sulfoxide (DMSO); thionyl chloride; sulfurylchloride, or a combination thereof. Among other advantages, the lowviscosity additive may improve the spreading speed of the electrolytewhen being printed. It will be appreciated that the disclosed additivescan be substantially electrochemically stable in combination of variousprinted electrochemical reactants described herein.

In some embodiments, the electrolyte includes a surfactant. For example,the surfactant may be nonionic. The nonionic surfactant that may beincluded as part of the electrolyte includes one or more of cetylalcohol, stearyl alcohol, and cetostearyl alcohol, oleyl alcohol,polyoxyethylene glycol alkyl ethers, octaethylene glycol monododecylether, glucoside alkyl ethers, decyl glucoside, polyoxyethylene glycoloctylphenol ethers, Triton® X-100 (sold by Sigma-Aldrich®), nonoxynol-9,glyceryl laurate, polysorbate, poloxamers, or a combination thereof.Among other advantages, the surfactant may improve the spreading speedof the electrolyte when being printed. It will be appreciated that thedisclosed additives can be substantially electrochemically stable incombination of various printed electrochemical reactants describedherein.

In some embodiments, the separator may include a filler material. Thefiller material may include one or more of diatom frustules, zeolites,cellulose fibers, fiberglass, alumina, silica gel, molecular sievecarbon, natural-clay based solids, polymeric absorbents or a combinationthereof, among other filler materials.

In some embodiments, the separator may include a polymer binder. Thepolymer binder may include one or more of polymers (or equivalently,polymeric precursors or polymerizable precursors) such as polyvinylpyrrolidone (PVP), polyvinyl alcohol (PVA), polyvinylidene fluoride,polyvynylidene fluoride-trifluoroethylene, polytetrafluoroethylene,polydimethylsiloxane, polyethelene, polypropylene, polyethylene oxide,polypropylene oxide, polyethylene glycolhexafluoropropylene,polyethylene terefphtalatpolyacrylonitryle, polyvinyl butyral,polyvinylcaprolactam, polyvinyl chloride; polyimide polymers andcopolymers (including aliphatic, aromatic and semi-aromatic polyimides),polyamides, polyacrylamide, acrylate and (meth)acrylate polymers andcopolymers such as polymethylmethacrylate, polyacrylonitrile,acrylonitrile butadiene styrene, allylmethacrylate, polystyrene,polybutadiene, polybutylene terephthalate, polycarbonate,polychloroprene, polyethersulfone, nylon, styrene-acrylonitrile resin;polyethylene glycols, clays such as hectorite clays, garamite clays,organo-modified clays; saccharides and polysaccharides such as guar gum,xanthan gum, starch, butyl rubber, agarose, pectin; celluloses andmodified celluloses such as hydroxyl methylcellulose, methylcellulose,ethyl cellulose, propyl methylcellulose, methoxy cellulose, methoxymethylcellulose, methoxy propyl methylcellulose, hydroxy propylmethylcellulose, carboxy methylcellulose, hydroxy ethylcellulose, ethylhydroxyl ethylcellulose, cellulose ether, cellulose ethyl ether,chitosan, or a combination thereof.

It will be appreciated that, while not illustrated for clarity, aprotective film may be formed on top of various ESDs disclosed herein toprovide mechanical, electrical and chemical protection to the ESDs fromthe outside world. The protective film may be, e.g., laminated orprinted. While the packaging of the ESDs are not discussed for brevity,it will be appreciated that the packaging forms an integral part of thethin film-based ESDs and thus part of finished products.

Thin Film-Based Energy Storage Device Configurations

As described above with respect to FIGS. 1 and 2A/2B, thin film-basedESDs include two general types, namely thin film-based ESDs havingvertically stacked electrode layers and current collectors, such as theexample ESD 100 described above with respect to FIG. 1, and thinfilm-based ESDs having laterally adjacent current collectors andelectrodes, such as the example ESD 200 described above with respect toFIGS. 2A/2B. As discussed above, each of the two general types of thinfilm-based ESDs can have certain advantages over the other of the twotypes of thin film-based ESDs. For example, ESDs having laterallydisposed current collectors and electrodes can be advantageous for beingcapable of being printed in fewer number of impressions or process stepsand accommodating greater layer thicknesses of the electrodes and/orcurrent collectors. On the other hand, ESDs having vertically disposedelectrode layers and current collectors can be advantageous for highercurrent capability due to larger areas of overlap between opposingelectrode layers and a shorter travel distance therebetween for ions. Inthe following, various embodiments of the two general types of thinfilm-based ESDs are disclosed, which can offer these and otheradvantages based in part on the physical arrangements of their componentlayers.

In various thin film-based ESDs, relative volumes and/or masses ofelectrode active materials maybe adjusted to be different betweenelectrode active materials of opposite polarities for several reasons.For example, in thin film-based ESDs such as batteries that involveelectrochemical reactions, relative amounts of first and secondelectrode active materials, e.g., cathode and anode active materials,may be adjusted to be different based on the electrochemical reactionunderlying the ESDs. For example, in thin film-based ESDs where a ratiobetween the amounts of the first electrode active material and thesecond electrode active material that participate in an electrochemicalreaction is about 1:1 on a molar basis, the first and second electrodeactive materials may be disposed in respective electrode layers at aratio of about 1:1 on a molar basis. However, in thin film-based ESDswhere the ratio of the amounts of the first electrode active materialand the second electrode active material that participate in theelectrochemical reaction is greater/less than 1:1 on a molar basis, ordue to various other structural and material differences between thefirst and second electrode active materials, the relative volumes and/ormasses of the first and second electrode active materials may beadjusted to be significantly different. In various embodiments, thevolumes and/or the masses of the electrode active materials can beadjusted by adjusting the areas and/or the thickness of the electrodes.FIGS. 3A and 3B illustrate a thin film-based ESD 300 in which thevolumes and/or masses of the active materials of the first and secondelectrode layers 112, 120 can be adjusted by adjusting at least thesurface areas of the first and second electrode layers 112, 120.

FIG. 3A illustrates a side view of a thin film-based energy storagedevice 300 having asymmetric laterally adjacent current collectors andelectrode layers, where the ratio of surface areas between the first andsecond electrode layers is adjusted in accordance with a molar ratio ofthe active materials. FIG. 3B illustrates a plan view of electrodelayers of the thin film-based energy storage device illustrated in FIG.3A. Similar to the ESD 200 illustrated with respect to FIGS. 2A and 2B,the ESD 300 includes first and second current collectors 108, 124 areformed laterally adjacent to each other on a substrate 104 and areseparated by a gap 210 in a lateral direction. The ESD 300 additionallyincludes a first electrode layer 112 and a second electrode layer 120formed over or on the first current collector 108 and the second currentcollector 124, respectively, and are also formed laterally adjacent toeach other and separated by the gap 210 in the lateral direction. Theseparator 120 is formed over or on the first and second electrodes 112,120. Unlike the ESD 200 of FIGS. 2A and 2B, however, the lateralfootprints or the surface areas of the first and second electrode layers112, 120 are different and asymmetric. In particular, the proportion ofthe surface areas of the first and second electrode layers 112, 120 isadjusted according to the stoichiometric ratios of the electrode activematerials of the first and second electrodes, e.g., cathode and anodeactive materials, according to the underlying electrochemical reaction,as described above. For example, when the ratio of the amounts of thefirst and second electrode active materials, e.g., cathode and anodeactive materials, involved in the underlying electrochemical reaction is1:1 on a molar basis, a ratio V₁/V₂ between a first volume V₁ of thefirst electrode layer 112 containing the first electrode active materialand a second volume V₂ of the second electrode layer 120 containing thesecond electrode active material may be proportional to a ratio m₁/m₂ ofthe first molar mass m₁ of the first electrode active material to thesecond molar mass m₂ of the second electrode active material, and to aratio ρ₂/ρ₁ of the second density ρ₂ of the second electrode activematerial to the first density ρ₁ of the second electrode activematerial. To adjust the ratio V₁/V₂, in some implementations, thesurface areas of the first and second electrode layers 112, 120 areadjusted while keeping their thicknesses relatively constant. In theseimplementations, when the ratio of the first and second electrode activematerials, e.g., cathode and anode active materials, involved in anelectrochemical reaction is 1:1 on the basis a molar ratio, ingeometries where the first and second electrode layers 112, 120 can beapproximated as rectangular slabs having approximately the samethicknesses, a ratio A₁/A₂ between a first surface area A₁ of the firstelectrode layer 112 and a second surface area A₂ of the second electrodelayer 120 may be proportional to the ratio m₁/m₂ and to the ratio ρ₂/ρ₁.

Still referring FIGS. 3A/3B, the first electrode layer comprises a firstelectrode active material and the second electrode layer comprises asecond electrode active material, wherein a molar ratio between thefirst electrode active material and the second electrode active materialis between 0.1 and 0.4, 0.4 and 0.7, 0.7 to 1.0, 1.0 to 1.3, 1.3 to 1.6,1.6 to 1.9, 1.9 to 2.2, 2.2 to 2.5, 2.5 to 2.8, 2.8 to 3.1, 3.1 to 3.4,3.4 to 3.7, 3.7 to 4.0, 4.0 to 4.3, or in a range defined by any ofthese values, where the molar ratio can correspond to the underlyingelectrochemical reaction of the ESD. For example, as an illustrativeexample, when the ESD comprises an alkaline battery in which the firstelectrode active material comprises zinc and the second electrode activematerial comprises MnO₂, the molar ratio between the first electrodeactive material and the second electrode active material can benominally about 0.5, e.g., between about 0.4 and 0.7. In anotherillustrative example, when the ESD comprises an alkaline battery inwhich the first electrode active material comprises zinc and the secondelectrode active material comprises Ag₂O, the molar ratio between thefirst electrode active material and the second electrode active materialcan be nominally about 1.0, e.g., between about 0.7 and 1.3.

In various thin film-based ESDs such as batteries that involveelectrochemical reactions, it may be desirable to shorten the distanceof travel of the ions involved in the underlying electrochemicalreaction between the electrode active materials of the first and secondelectrode layers 112, 120, while limiting the number of deposition stepsor printing impressions low, e.g., four steps or impressions. It mayalso be desirable to increase the area of overlap between the first andsecond electrode layers 112, 120 to increase the current while andkeeping the degrees of freedom with respect to being able to adjustingthe volumes of electrode active materials as described above withrespect to FIG. 3. To address these and other needs, an ESD can beconfigured as a thin film-based ESD 400 illustrated with respect to FIG.4, according to embodiments. FIG. 4 illustrates a side view of a thinfilm-based ESD 400 having laterally adjacent current collectors andelectrode layers that have overlapping portions in the verticaldirection. Similar to the ESD 300 illustrated with respect to FIGS.3A/3B, the ESD 400 includes a first current collector 108 and a secondcurrent collector 124 formed over or on a substrate 104 and adjacentlydisposed and separated by a gap in a lateral direction. Also similar tothe ESD 300 (FIGS. 3A, 3B), the ESD 400 has a first electrode 112 formedover the first current collector 108. However, unlike the ESD 300illustrated in FIGS. 3A/3B, in the ESD 400, the separator 116 is formedon or over the first electrode layer 112 and the first current collector108, prior to forming the second electrode 120, while leaving a portionof the second electrode 124 exposed for forming thereon the secondelectrode layer 120. Thereafter, the second electrode 120 is formed overthe separator 116 and over the second current collector 124. The secondelectrode layer 120 comprises a base portion 120B extending from thesecond current collector 124 in a vertical direction and a lateralextension portion 120A laterally extending from the base portion in thelateral direction to overlap the first electrode layer 112. The baseportion 120B and the lateral extension portion 120A directly contactsthe vertical and lateral surfaces of the separator 116. The electrodeconfiguration of the ESD 400 offers various advantages.

In operation, when a voltage is applied between the first currentcollector 108 and the second current collector 124, ions may beexchanged between the first electrode layer 112 and the second electrodelayer 120 through the separator 116, thereby charging or discharging theESD 400. Advantageously, a substantial or a predominant portion of theionic exchange may occur in a vertical direction between overlappingportions of the first electrode layer 112 and the second electrode layer120. Thus, advantageously, in a similar manner as described above withrespect to the ESD 100 of FIG. 1, the area of overlap between the firstelectrode 112 and the second electrode 120 can be controlled to adjustthe amount of ionic current during charge/discharge. For example, bysubstantially laterally overlapping the lateral extension portion 120Aof the second electrode layer 120 and the first electrode layer 112, theoverlapping area available of ionic conduction between the first andsecond electrode layers 112 and 120 can be correspondingly increased,thereby enabling higher current, higher power and/or faster charging ofthe ESD 400.

In addition to the higher ionic current, the electrode configuration ofthe ESD 400 can advantageously allow for flexible adjustment of therelative amounts or volumes of the first and second electrode layers112, 120 according to a stoichiometric ratio of the respective electrodeactive materials involved in the underlying electrochemical reaction ofthe ESD 400. For example, depending on the volume (area and thickness)of the first electrode layer 108 formed on the first current collector108, the amount of the second electrode layer 120 can be adjusted byadjusting the width (w₁) 404 of the base portion 120B as well as thethickness (t₁) 408 of the lateral extension portion 120A.

The inventors have discovered that the electrode configuration of theESD 400 can be optimized to enhance the ionic conduction between thefirst and second electrode layers 108, 120, as well as the electronicconduction in the second electrode 120 by adjusting a ratio between thewidth (w₁) 404 of the base portion 120B and the thickness (t1) 408 ofthe lateral extension portion 120A. In various embodiments, an effectiveratio w₁/t₁ for obtaining various desirable operational parametersdescribed herein, including the current and voltage of the ESD, can bein a range defined by any of two of 1:1, 2:1, 3:1, 4:1, 5:1, 6:1, 7:1,8:1, 9:1 and 10:1 or greater.

As described above, the capacity of an ESD can depend on, among otherthings, the volumes of the electrode layers. One way to increase thecapacity is to increase the volumes of the electrode layers, for a giventhickness, by increasing the coverage areas of the electrode layers.However, increasing the coverage areas of the electrode layers, may notbe desirable or practical, as increasing the coverage areas of some thinfilm-based ESDs, e.g., ESDs having laterally adjacent electrode layerssuch as the ESD 200 described above with FIGS. 2A/2B, directly increasesthe overall device footprint. One way to increase the battery capacitywithout increasing the overall device footprint, is to deposit thickerelectrode layers. However, it will be appreciated that, thickerelectrode layers can be more prone to cracking or delamination due to,the film stress that is proportional to the film thickness. The cracksor delamination can cause various problems, e.g., reduction in batterycapacity, as well as safety concerns. In the following, variousconfigurations of ESDs are described, which can increase the capacity ofthe ESD while mitigating one or more of these potential downsides.

FIG. 5 illustrates a side view of a thin film-based energy storagedevice (ESD) 500 having laterally adjacent current collectors andelectrode layers, where the electrode layers are formed on opposingmajor surfaces of a perforated separator, for increased capacity withoutincreasing the overall lateral footprint of the thin film-based ESD.FIG. 6 illustrates a plan view of thin film-based energy storage deviceillustrated in FIG. 5. In particular, to further increase the capacityof the ESD by increasing the volume and/or mass of the electrode layers,the ESD 500 comprises one or both of the first and second electrodes512, 520 that are formed on opposing sides of a perforated separator516. The ESD 500 has various features that are analogous to the ESD 300(FIGS. 3A/3B) described above, including adjacently disposed first andsecond current collectors 108, 124 formed over or on a substrate 104,first and second electrodes 512A, 520A adjacently formed thereover orthereon, respectively, and the separator 516 that is formed over or onthe first and second electrode layers 512A, 520A. The details offeatures that are analogous to those described with respect to FIGS.3A/3B are omitted herein for brevity. Similar to the ESD 300 describedabove, the first and second electrode layers 512A, 520A are formedbetween the separator 516 and the first and second current collectors108, 124, respectively. The capacity of ESD 500 can be adjusted byadjusting the respective lateral coverage areas of the first and secondelectrode layers 512A, 520A. However, unlike the ESD 300 (FIGS. 3A/3B),the separator 516 comprises perforations or openings 506 formedtherethrough over the first electrode layer 512A and perforations oropenings 502 formed therethrough over the second electrode layer 520A.In addition, additional first and second electrode layers 512B, 520B areformed over or on the outer surface of the separator 516. Thus, thefirst electrode 512 comprises first and additional first electrodelayers 512A, 512B formed on opposing sides of the separator 516, and thesecond electrode 520 comprises second and additional second electrodelayers 520A, 520B formed on opposing sides of the separator 516. The twolayers of each of the first and second electrodes 512, 520 can be formedby, e.g., depositing or printing twice, once on the respective ones ofthe current collectors 108, 124, and a second time on the separator 516.To provide electrical and ionic continuity between the electrode layersand the additional electrode layers, the openings or perforations 502may be filled when the additional second electrode layer 520B isdeposited or printed, and the openings or perforations 506 may be filledwhen the additional first electrode layer 512B is deposited or printed.The first electrode active material of the first electrode 512 fills theperforations 506 to electrically connect the first and additionalelectrode layers 512A, 512B of the first electrode 512 formed onopposing sides of the separator 516, and the second electrode activematerial of the second electrode 520 fills the perforations 502 toelectrically connect the second and additional second electrode layers520A, 520B of the second electrode layer formed on opposing sides of theseparator 516. Thus, as configured, relative to ESD configurations inwhich the electrode layers are formed only on one side of the separator(e.g., ESD 300 of FIG. 3), the ESD 500 can have higher capacity for thesame lateral footprint of the ESD 500. For example, if the combinedvolumes and/or masses of the electrode active materials of the first andsecond electrodes 512, 520 are doubled with respect to those of the ESD300 (FIGS. 3A/3B), the capacity can approximately be correspondinglydoubled. In addition, because the individual layer thicknesses ofelectrode layers are not proportionally increased, the built-up stressin the electrode layers can be kept at relatively low values, therebyachieving the higher capacity without a proportionally increased risk ofcracking or delamination.

Still referring to FIG. 5, it will be appreciated that the shape anddensity of the openings or perforations 502, 506 may be adjusted tosufficiently facilitate the electronic and ionic conduction between theelectrode layers on the opposing sides of the separator 516.Furthermore, the shape and size of the openings or perforations 502, 506may be suitably selected depending on the printing process employed. Theshape and size of the openings or perforations 506 may be suitablyselected such that, when the additional first electrode layer 512B isprinted on the separator 516, the perforations or openings 506 aresufficiently filled with the ink of the addition first electrode layer512B. Similarly, the shape and size of the openings or perforations 502may be suitably selected such that, when the additional second electrodelayer 520B is printed on the separator 516, the perforations or openings506 are sufficiently filled with the ink of the addition first electrodelayer 512B. For example, the openings or perforations 502, 506 may havean average size of 0.1 mm to 0.5 mm, 0.5 mm to 1.0 mm, 1.0 mm to 1.5 mm,1.5 mm to 2.0 mm, 2.0 mm to 2.5 mm, 2.5 mm to 3.0 mm, 3.0 mm to 3.5 mm,3.5 mm to 4.0 mm, 4.0 to 4.5 mm, 4.5 mm to 5.0 mm, or in a range definedby any of these values. The openings or perforations 502, 506 mayfurther be formed such that an average inter-opening distance may beaverage size ranging from 0.5 mm to 1.0 mm, 1.0 mm to 1.5 mm, 1.5 mm to2.0 mm, 2.0 mm to 2.5 mm, 2.5 mm to 3.0 mm, 3.0 mm to 3.5 mm, 3.5 mm to4.0 mm, 4.0 to 4.5 mm, 4.5 mm to 5.0 mm, or in range defined by any ofthese values. The openings or perforations 502, 506 may have anysuitable shape such as polygonal or circular shapes. Other openingsizes, inter-opening distances and shapes are also possible.

As described above, volumes and/or masses of the electrode activematerials of the first and/or second electrode layers of a thinfilm-based ESD can be increased for a given area by forming electrodelayers on both sides of a perforated separator. In a similar manner, thevolumes and/or masses of the first and/or second electrode layers of athin film-based ESD can be increased for a given area by formingelectrode layer one or both sides of a current collector, e.g., aperforated current collector. FIG. 7 illustrates a side view of a thinfilm-based energy storage device 700 having current collectors andelectrode layers that are vertically stacked, where electrode layers areformed on opposing major surfaces of a current collector, e.g., aperforated current collector, for increased capacity without increasingthe overall lateral footprint of the thin film-based ESD. The ESD 700has some features that are analogous to the ESD 100 (FIG. 1) describedabove, including the relative arrangements of different layers includinga substrate 104 on which a first current collector 108, a firstelectrode layer 112, a separator 116, a second electrode 720 and asecond current collector 124 are formed in a stack configuration. Thedetails of features that are analogous to those of FIG. 1 are omittedherein for brevity. Similar to the ESD 100 described above, the secondelectrode layer 720B is formed between the separator 116 and the secondcurrent collector 124. The capacity of ESD 700 can be adjusted byadjusting the respective lateral coverage areas of the first and secondelectrode layers 112, 720B. However, unlike the ESD 100 (FIG. 1), thesecond electrode 720 comprises an additional second electrode layer 720Aformed over or on the outer surface of the second current collector 124.Thus, the second electrode 720 comprises the second electrode layer 720Band the additional second electrode layer 720A that are formed onopposing sides of the second current collector 124, which may beperforated. The two layers of the second electrode 720 can be formed by,e.g., depositing or printing twice, once on the separator 116 and asecond time on the second current collector 124. To provide electricaland ionic continuity between the second electrode layer 720B and theadditional second electrode layer 720A, the second current collector 124has a plurality of openings or perforations 702 that are formedtherethrough. The openings or perforations 702 may be filled when theadditional second electrode layer 720A is deposited or printed, therebyallowing for electron and ionic transfer between the second electrodelayer 720B and the additional second electrode layer 720A of the secondelectrode 720 that are formed on opposing sides of the second currentcollector layer 124. Thus, as configured, relative to ESD configurationsin which the electrode layers are formed only on one side of the currentcollector (e.g., ESD 100 of FIG. 1), the ESD 700 can have highercapacity for the same lateral footprint of the ESD. In addition, becausethe individual layer thicknesses of the second electrode layer 720B andthe additional second electrode layer 720A are not proportionallyincreased, the built-up stress in the electrode layers can be kept atrelatively low values, thereby achieving the higher capacity without aproportionally increased risk of cracking or delamination.

The openings or perforations 702 can have the shape, density and sizethat are similar to those described above with respect to FIGS. 5 and 6.

In some embodiments, the capacity of the ESD can be increased withoutincreasing the device footprint by stacking a plurality of first andsecond electrode layers to form more than one ESD unit or cell, andelectrically connecting then in parallel. FIG. 8 illustrates a side viewof a thin film-based energy storage device 800 having vertically stackedcurrent collectors and electrode layers, where two first electrodelayers, two second electrode layers and two separators are configured astwo energy storage devices electrically connected in parallel, forincreased capacity without increasing the overall lateral footprint ofthe thin film-based ESD. The ESD 800 has some features that areanalogous to the ESD 100 (FIG. 1) described above, including a substrate104 on which a first portion 808A of a first current collector 808, afirst electrode layer 112 a first separator 116, a second electrodelayer 120 and a second current collector 124 are successively formed ina stack configuration. The details of stack that are analogous to thoseof FIG. 1 are omitted herein for brevity. Unlike the ESD 100 (FIG. 1),the ESD 800 additionally includes additional successively formed layersincluding an additional second electrode layer 820, a second separator816 and an additional first electrode layer 812, and a second portion808B of the first current collector 808 are further successively formedas a stack. The first and second portions 808A, 808B are electricallyconnected as a single first current collector 808 on which the first andadditional first electrode layers 112, 812 are formed. The second andadditional second electrode layers 120, 820 are formed on the secondcurrent collector 124, which are separated from the first and additionalfirst electrode layers 112, 812 by the first and second separators 116,816, respectively. Thus, as configured, the ESD 800 comprises two ESDunits or cells formed on opposing sides of the second current collector124 that are electrically connected in parallel. Thus, relative to ESDconfigurations in which a single stack of layers is formed (e.g., ESD100 of FIG. 1), the ESD 800 can have higher capacity for the samelateral footprint of the ESD. In addition, because the individual layerthicknesses of the first and second electrode layers 112, 120 and theadditional first and second electrode layers 812, 820 are notproportionally increased, the built-up stress in the electrode layerscan be kept at relatively low values, thereby achieving the highercapacity without a proportionally increased risk of cracking ordelamination.

Still referring to FIG. 8, in other embodiments, while not illustrated,the capacity of the ESD 800 can be further increased by configuring thesecond portion 808B of the first current collector 808 to haveperforations or openings formed therethrough, in a similar manner asdescribed above with respect to the second current collector 124 of theESD 700 of FIG. 7.

In some embodiments, the capacity of the ESD can be increased by havinga plurality of first and second electrodes on both sides of a substrate.Accordingly, FIG. 9 illustrates a side view of a thin film-based energystorage device 900 having laterally adjacent current collectors andelectrode layers, where the current collector layers and the electrodelayers are formed on opposing surfaces of a substrate, e.g., aperforated substrate, for increased capacity without increasing theoverall lateral footprint of the thin film-based ESD. In the illustratedembodiments, the substrate 904 has a plurality of perforations oropenings 902, 906 formed therethrough. On each side of the perforatedsubstrate 904, various layers that are analogous to the ESD 300 (FIGS.3A/3B) described above are formed, including adjacently disposed firstand second current collectors formed on a substrate, adjacently disposedfirst and second electrode active layers and a separator formed over thefirst and second electrode layers. Accordingly, the first currentcollector 908 comprises a first current collector layer 908A and anadditional first current collector layer 908B formed on opposing sidesof the substrate 904. The first and additional first current collectorlayers 908A, 908B of the first current collector 908 are electricallyconnected through the plurality of openings or perforations 902 formedtherethrough. In a similar manner, the second current collector 924comprises a second current collector layer 924A and an additional secondcurrent collector layer 924B formed on opposing sides of the substrate904. The second and additional second current collector layers 924A,924B of the second current collector 924 are electrically connectedthrough the plurality of openings or perforations 906 formedtherethrough.

Still referring to FIG. 9, on the first side of the substrate 904, afirst electrode layer 112A is formed on the first current collectorlayer 908A of the first current collector 908, and on the second side ofthe substrate 904, an additional first electrode 112B is formed on theadditional first current collector layer 908B of the first currentcollector 908. In a similar manner, on the first side of the substrate904, a second electrode layer 120A is formed on the second collectorlayer 924A of the second current collector 924, and on the second sideof the substrate 904, an additional second electrode layer 120B isformed on the additional second collector layer 924B of the secondcurrent collector 924. The separator 116 comprises a first separatorlayer 116A formed on the first side of the substrate 904 to cover thefirst electrode layer 112A and the second electrode layer 120A, and asecond separator layer 116B formed on the second side of the substrate904 to cover the additional first electrode layer 112B and theadditional second electrode layer 120B. The first and second separatorlayers 116A, 116B of the separator 116 are connected through the gap 210formed between the first and second current collectors 908, 924, betweenthe first electrode layer 112A and the second electrode layer 120A, andbetween the additional first electrode layer 112B and the additionalsecond electrode layer 120B.

To manufacture the ESD 900, the two layers of the first currentcollector 908 can be formed by, e.g., depositing or printing twice, onceon the first side of the substrate 904 and a second time on the secondside of the substrate 904. The openings or perforations 902 may befilled when either or both of the first current collector layer 908A andthe additional first current collector layer 908B are deposited orprinted, thereby allowing for electronic continuity between the firstcurrent collector layer 908A and the additional first current collectorlayer 908B that are formed on opposing sides of the substrate 904.Similarly, the two layers of the second first current collector 924 canbe formed by, e.g., depositing or printing twice, once on the first sideof the substrate 904 and a second time on the second side of thesubstrate 904. The openings or perforations 906 may be filled wheneither or both of the second current collector layer 924A and theadditional second current collector layer 924B are deposited or printed,thereby allowing for electronic continuity between the second currentcollector layer 924A and the additional second current collector layer924B that are formed on opposing sides of the substrate 904. Thereafter,first and additional first electrode layers 112A, 112B are formed on thefirst and additional first current collector layers 908A, 908B of thefirst current collector 908, respectively, and second and additionalsecond electrode layers 120A, 120B are formed on the second andadditional second current collector layers 924A, 924B of the secondcurrent collector 924, respectively. The separator 116 can be formed inone of four ways: (a) on one of two sides of the substrate 904, (b) onone side of the substrate 904 and through the gap 210 to reach the otherside of the substrate 904; (c) on both sides of the substrate 904; and(d) on both sides of the substrate 904 and through the gap 210. Thus, asconfigured, relative to ESD configurations in which the electrode layersare formed only on one side of the substrate (e.g., ESD 300 of FIGS.3A/3B), the ESD 900 can have higher capacity for the same lateralfootprint of the ESD. The openings or perforations 902 formed in thesubstrate 904 between the layers of the first current collector 908, theopenings or perforations 906 formed in the substrate 904 between thelayers of the second current collector 924 can have the size, theinter-opening distances, shapes and any other characteristics describedabove with respect to the openings or perforations formed through theseparator as described in FIGS. 5 and 6. While not illustrated, thecapacity of the ESD 900 can be further increased by configuring thefirst and second separator layers 116A, 116B of the separator 116 tohave perforations formed therethrough, followed by forming furtherlayers of the first and second electrodes on the first and secondseparator layers 116A, 116B, and in the perforations formedtherethrough, in a similar manner as described above with respect to theESD 500 of FIGS. 5 and 6.

It will be appreciated that the electrode layer arrangements of the ESDsdescribed above with respect to FIGS. 5-9 advantageously provide, inaddition to tuning relative amounts or volumes of the individual activematerials of the first and second electrode layers, an additional degreeof freedom for adjusting the molar ratio between active materials of thefirst and second electrode layers, without substantially increasing theoverall lateral footprint of the ESDs. The arrangements can beparticularly beneficial in implementations of thin film-based ESDs wherethe molar ratio between the first electrode active material and thesecond electrode active material is substantially greater or less than1.0, e.g., greater than 1.3 or less than 0.7.

Electrode and Current Collector Shapes for Enhanced Electrode Overlap inThin Film-Based Energy Storage Devices

As described above, e.g., with respect to FIGS. 2A/2B, when a voltage isapplied between current collectors in ESDs having laterally disposedelectrode layers, a substantial portion of the ionic exchange may occurin a lateral direction. For example, the ionic exchange may occurbetween overlapping surfaces of the electrode layers, e.g., betweenoverlapping surfaces of the first electrode layer 112 and the secondelectrode layer 120 in the lateral direction across the gap 210 in theillustrated ESD 200 in FIGS. 2A/2B. The inventors have discovered thathigher ionic exchange may be achieved in various ESDs by increasing thearea of overlap between the electrode layers. In the following, variousembodiments of ESDs are configured to enhance the ionic exchange betweenthe electrodes by increasing the overlap area between the electrodes forhigher current, higher current density and/or shorter charging times.

FIGS. 10A-10E illustrate plan views of different electrode overlaparrangements 1000A-1000E of thin film-based energy storage deviceshaving laterally adjacent current collectors and electrode layers, wherethe first and second electrodes have different shapes and for differentamounts of overlap area therebetween. Each of the electrode overlaparrangements 1000A-1000E include a first electrode layer 112 and asecond electrode layer 120 that are laterally disposed relative to eachother, in a similar manner as described above with respect to, e.g.,FIGS. 3A/3B). In the electrode overlap arrangement 1000A illustrated inFIG. 10A, each of the first and second electrode layers 112, 120 arerectangular in shape and are elongated in a first lateral directione.g., the horizontal direction, and have widths that overlap in thefirst lateral direction. In the electrode overlap arrangement 1000B ofFIG. 10B, each of the first and second electrode layers 112, 120 arerectangular in shape and are elongated in a second lateral direction,e.g., the vertical direction, and have lengths that overlap in thesecond lateral direction. In the electrode overlap arrangement 1000C ofFIG. 10C, each of the first and second electrode layers 112, 120 has astrap portion and a plurality of regularly spaced rectangularprotrusions or fingers, where the rectangular protrusions or fingers ofthe first and second electrode layers 112, 120 are interlaced orinterleaved such that they alternate in a lateral direction, e.g., thehorizontal direction, for increased overlapping edge lengths of thefirst and second electrode layers 112, 120. In the electrode overlaparrangement 1000D of FIG. 10D, each of the first and second electrodelayers 112, 120 has a strap portion and a plurality of regularly spacedrounded protrusions or fingers, where the rounded protrusions or fingersof the first and second electrode layers 112, 120 are interlaced orinterleaved such that they alternate in a lateral direction, e.g., thehorizontal direction, for increased overlapping edge lengths of thefirst and second electrode layers 112, 120. In the electrode overlaparrangement 1000E of FIG. 10E, each of the first and second electrodelayers 112, 120 has a strap portion and a plurality of regularly spacedprotrusions, fingers, tines or spikes, where the elongated protrusions,fingers, tines or spikes of the first and second electrode layers 112,120 are interlaced or interleaved such that they alternate in a lateraldirection, e.g., the horizontal direction, for increased overlappingedge lengths of the first and second electrodes.

To show the effect of the different electrode overlap arrangements onthe resulting ion exchange, batteries having the different electrodeoverlap arrangements as illustrated in FIGS. 10A-10E were fabricated byprinting. To directly compare the resulting electrical characteristicsof the batteries, each of the different batteries having the differentarrangements 1000A-1000E were printed to have the same lateral coverageor surface area of the respective first electrode layer 112 of the firsttype and the respective second electrode layer 120 of the second type.In addition, the different batteries having the different electrodeoverlap arrangements 1000A-1000E were printed to have the samethicknesses, the same coverage or surface areas of the first electrodelayer 112 and the same coverage or surface areas of the second electrodelayer 120. In addition, the different batteries having the differentelectrode overlap arrangements 1000A-1000E were printed to have samewidths of the gaps 210 between the first and second electrode layers112, 120. Thus, the electrical characteristics were compared fordifferent batteries arrangements 1000A-1000E with respect to lengths ofoverlap, which is equivalent to the areas of overlap, between first andsecond electrode layers 112, 120 across the gaps 210 as the variable. Ineach of the fabricated batteries, the first and second electrode layers112, 120 were printed on respective current collectors, and a separatorhaving the same electrolyte composition was deposited on top of theelectrode layers 112, 120 to fill the gap 210 therebetween, in a similarmanner as described above with respect to the ESD 200 (FIGS. 2A/2B). Theresistance was measured between the current collectors for on each ofthe batteries having the different electrode arrangements 1000A-1000Eusing a step current method. The measured resistance values for the ESDshaving different electrode overlap arrangements 1000A-1000E are shown inTABLE 1, as a function of the length of overlap between the first andsecond electrode layers 112, 120. One can clearly see that theresistance is inversely proportional to the length of overlap betweenthe first and second electrode layers 112, 120.

TABLE 1 Experimental Correlation Between Overlap Length BetweenElectrodes and Battery Resistance Length of Overlap Between ResistanceElectrode Arrangement Electrodes (cm) (Ohms) Horizontal Rectangular(FIG. 10A) 1.4 1222 Vertical Rectangular (FIG. 10B) 2.5 698 InterlacingStrapped Rectangular Protrusions 10.2 371 (FIG. 10C) InterlacingStrapped Rounded Protrusions 11.4 335 (FIG. 10D) Interlaced StrappedFingers (FIG. 10E) 59.9 150

The experimental measurements of the resistance of the batteries havingdifferent electrode overlap arrangements 1000A-1000E show that the ionicexchange, as measured by ion current density, shows a clear dependenceon the length of the overlap, which is equivalent to the area ofoverlap, between the first and second electrode layers 112, 120. Thus,based the observed relationship between the overlap area and theresistance, the inventors have determined that electrode overlaparrangements having relatively large amount of overlap between theelectrodes may be employed in applications where relatively highercurrent, higher power and/or faster charge rates are desired. On theother hand, electrode overlap arrangements having relatively smallamount of overlap between the electrodes may be employed in applicationswhere relatively lower current, lower power and/or lower self-dischargerates are desired.

Still referring to FIGS. 10A-10E, it will be appreciated that, while ineach of the illustrated electrode overlap arrangements 1000A-1000E, thefirst and second electrode layers 112, 120 have the same footprints orsurface areas, embodiments are not so limited. In other embodiments, ineach of the illustrated electrode overlap arrangements 1000A-1000E, theratio of the footprints or surface areas can be adjusted according tothe molar ratio associated with the electrochemical reaction between theelectrode active materials. For example, as described above with respectto FIGS. 3A and 3B, the surface areas of the first and second electrodeslayers 112, 120 may be adjusted to be different, according to thestoichiometric ratios of the cathode and anode active materials. Asdescribed above, as an illustrative example, when the thicknesses of thefirst and second electrode layers 112, 120 are about the same and whenthe ratio of the amounts of the first and second electrode activematerials, e.g., cathode and anode active materials, associated with theelectrochemical reaction is 1:1 on the basis of a molar ratio, a ratioA₁/A₂ of a first coverage or surface area A₁ of the first electrodelayer 112 to a second surface area A₂ of the second electrode layer 120may be proportional to a ratio m₁/m₂ of the first molar mass m₁ of thefirst electrode active material to the second molar mass m₂ of thesecond electrode active material, and to a ratio ρ₂/ρ₁ of the seconddensity ρ₂ of the second electrode active material to the first densityρ₁ of the second electrode active material. By way of example, FIGS. 11Aand 11B illustrate plan views of electrode overlap arrangements of athin film-based ESD in which first and second electrode layers 112, 120have the same and different surface areas, respectively. FIG. 11Aillustrates a plan view of an electrode arrangement of a thin film-basedenergy storage device 1100A having laterally adjacent current collectorsand electrode layers, similar to the arrangement illustrated in FIG.10E, where the first and second electrode layers 112, 120 have about thesame surface area. Each of the first and second electrode layers 112,120 has a strap portion and a plurality of regularly spaced fingers orprotrusions, where the fingers or protrusions of the first and secondelectrode layers 112, 120 alternate in a horizontal direction. On theother hand, FIG. 11B illustrates a plan view of an electrode arrangementof a thin film-based energy storage device 1100B having laterallyadjacent current collectors and electrode layers, similar to thearrangement illustrated in FIG. 11A, except that the first and secondelectrode layers 112, 120 have different surface areas, and where theratio of surface areas between the first and second electrode layers112, 120 is adjusted in accordance with a molar ratio of the activematerials associated with the electrochemical reaction. In theillustrated embodiment, the second electrode layer 120 has a largerfootprint compared to the first electrode layer 112.

FIGS. 12A-12D illustrate plan views of intermediate structures1200A-1200D at various stages of fabricating a thin film-based energystorage device 1200D having laterally adjacent current collectors andelectrode layers, similar to the arrangement illustrated in FIG. 10E,that are configured for increased ionic exchange and current, in asimilar manner as described above with respect to FIGS. 11A and 11B. Theresulting ESD 1200D has an electrode overlap arrangement similar to thatillustrated in FIGS. 11A and 11B. FIG. 13 illustrates a cross-sectionalview of the ESD 1200D of FIG. 12D through the section 12-12′. Referringto FIG. 12A, the intermediate structure 1200A illustrates as-depositedor as-printed first and second current collectors 108, 124, where eachof the laterally adjacent first and second current collectors 108, 124has a tab, a strap portion and a plurality of regularly spaced fingersor protrusions that are integrated as a single thin film layer, e.g., aprinted thin film layer. The fingers or protrusions of the first andsecond current collectors 108, 124 alternate in the first lateraldirection, e.g., the horizontal direction. The intermediate structure1200B of FIG. 12B illustrates the intermediate structure 1200A of FIG.12A after a first electrode layer 112 deposited, e.g., printed, over oron the first current collector 108. The intermediate structure 1200C ofFIG. 12C illustrates the intermediate structure 1200B of FIG. 12B aftera second electrode layer 120 is deposited, e.g., printed, over or on thesecond current collector 124. As illustrated, the first electrode layer112 generally follows the lateral contours of the first currentcollector 108, and the second electrode layer 120 generally follows thelateral contours of the second current collector 124. As describedabove, e.g., with respect to FIGS. 2A/2B, fingers or protrusions of oneor both of the first and second electrode layers 112, 120 can have alateral width that is about the same narrower than the fingers orprotrusions of the underlying first and second current collectors 108,124, respectively. Thus, each of the first and second electrode layers112, 120 has a strap portion and a plurality of regularly spaced fingersor protrusions, where the fingers of the first and second electrodesalternate in a first lateral direction, e.g., the horizontal direction,in a similar manner as described above with respect to FIGS. 10E, 11Aand 11B. The intermediate structure 1200D of FIG. 12 illustrates theintermediate structure 1200C of FIG. 12C after a separator 112 isdeposited or printed over or on the first and second electrode layers112, 120 and to fill the gap 210 formed therebetween. As illustrated inFIG. 12D, the separator layer 116 may be blanket deposited or printed.As illustrated in FIG. 13 illustrating a cross-sectional view of the ESD1200D through the section 12-12′ of the plan vie of the ESD 1200Dillustrated in FIG. 12D, the fingers of the first and second electrodelayers 112 and 120 formed over corresponding fingers of the first andsecond current collectors 108, 124, respectively, alternate in ahorizontal direction, where adjacent fingers of the first and secondelectrode layers 112 and 120 are separated by a gap 210 therebetween.

In operation, when a voltage is applied between the first currentcollector 108 and the second current collector 124, ions may beexchanged between the first electrode layer 112 and the second electrodelayer 120 through the separator 116, where, because of the lateralarrangement of the first and second electrode layers 112, 120, asubstantial or a predominant portion of the ionic exchange may occur ina lateral direction, e.g., between overlapping portions of the sidesurfaces of the fingers of the first electrode layer 112 and the fingersof the second electrode layer 120 across the plurality of gaps 210.Because of the increased length of overlap between the first electrodelayer 112 and the second electrode layer 120, the ionic conduction canbe greatly enhanced, as experimentally demonstrated with respect toTABLE 1 and FIGS. 10A-10E.

FIGS. 14A-14D illustrate plan views of intermediate structures1400A-1400D at various stages of fabricating a thin film-based energystorage device 1400D having laterally adjacent current collectors andelectrode layers that have overlapping portions in the verticaldirection and are configured for increased ionic exchange and current.FIG. 15 illustrates a cross-sectional view of the ESD 1400D illustratedin FIG. 14D through the section 14-14′. Referring to FIG. 14A, theintermediate structure 1400A illustrates as-deposited or as-printedfirst and second current collectors 108, 124, where each of thelaterally adjacent first and second current collectors 108, 124 has atab, a strap portion and a plurality of regularly spaced fingers orprotrusions that are integrated as a single thin film layer, e.g., aprinted thin film layer. Similar to FIG. 12A, the fingers or protrusionsof the first and second current collectors 108, 124 alternate in thefirst lateral direction, e.g., the horizontal direction. Theintermediate structure 1400B of FIG. 14B illustrates the intermediatestructure 1400A of FIG. 14A after a first electrode layer 112 isdeposited, e.g., printed, over or on the first current collector 108. Asdescribed above, e.g., with respect to FIG. 4, the fingers of the firstelectrode layer 112 can have lateral widths that are narrower than theunderlying fingers of the first current collector 108. The intermediatestructure 1400C of FIG. 14C illustrates the intermediate structure 1400Bof FIG. 14B after a separator layer 116 is deposited, e.g., printed,over or on the first electrode layer 112. As illustrated, the separatorlayer 116 generally follows the lateral contours of and encapsulates toelectrically separate the first electrode layer 112 and the firstcurrent collector 108. The intermediate structure 1400D of FIG. 14illustrates the intermediate structure 1400C of FIG. 14C after a secondelectrode layer 120 is deposited or printed over or on to cover theseparator layer 116 and the second current collector 124, and to fillthe gaps between adjacent fingers of the first electrode layer 112. Asillustrated in FIG. 14D, the second electrode layer 120 may beblanket-deposited. As illustrated in FIG. 15 representing across-sectional view of the ESD 1400D through the section 14-14′illustrated with respect to the intermediate structure 1400D of FIG.14D, the separator layer 116 covers or encapsulates the fingers formedby the stack of the first current collector 108 and the first electrodelayer 112. The second electrode layer 120 is formed on the fingers ofthe second current collector 124 and fills the gaps formed betweenseparator-covered fingers of the first electrode layer 112, such thatthe fingers first electrode layer 112 and the second electrode layer 120filling the gaps formed between adjacent ones of the fingers of thefirst electrode layers 112 alternate in a horizontal direction.

In operation, when a voltage is applied between the first currentcollector 108 and the second current collector 124, ions may beexchanged between the first electrode layer 112 and the second electrodelayer 120 through the separator 116, where, because of the separatorlayer 116 formed over the top and side surfaces of or encapsulates theplurality of the fingers of first electrode layer 112, the ionicexchange between the first and second electrode layers 112, 120 mayoccur in a vertical direction between fingers of the first electrodelayer 112 and portions of the second electrode layer 120 disposedthereover, and in lateral directions between fingers of the firstelectrode layer 112 and portions of the second electrode layer 120filling gaps formed between adjacent ones of the fingers of the firstelectrode layer 112. Because of the increased overlap between the firstelectrode layer 112 and the second electrode layer 120, the ionicconduction can advantageously be greatly enhanced, at least by amountsexperimentally demonstrated with respect to TABLE 1 and FIGS. 10A-10E.

In addition to the higher ionic conduction, the electrode configurationof the ESD 1400D can advantageously allow for flexible adjustment of therelative amounts or volumes of the first and second electrode layers112, 120 according to a stoichiometric ratio of the respective electrodeactive materials involved in the underlying electrochemical reaction ofthe ESD 1400D, in a similar manner as described above with respect toFIG. 4.

Serially Connected Thin Film-Based Energy Storage Devices

Among others, an advantage of using thin film-based depositiontechniques such as printing for fabricating energy storage devices isthe ability to form a plurality of patterned structures simultaneously,e.g., as part of the same impression. As a result, such thin film-basedtechniques are advantageous for fabricating a plurality of electricallyconnected ESD units or cells using the same number of printing steps orimpressions as in fabricating a single unit of ESD. For example, byprinting, a plurality of current collectors and electrode layers can besimultaneously formed and electrically connected in-situ, instead offorming individual current collectors or electrode layers andelectrically connecting them afterwards. By electrically connecting oneor more ESD cells or units in series, the net operational output voltagecan be customized for different applications, because the net ESDvoltage is proportional to the sum of the output voltages of the numberof ESDs in series. By electrically connecting one or more ESD cells orunits in parallel, the net operational capacity can be customized fordifferent applications, because the net ESD capacity is proportional tothe sum of the capacities of the number of ESD cells or units inparallel. Thus, by printing a plurality of ESD cells or units in seriesand/or in parallel, an ESD having customized operational voltage and/orcapacity can be fabricated with the same number of printing steps andimpressions as printing a single cell or unit of ESD. In the following,various embodiments are described in which a plurality of ESD units orcells are electrically connected in series or in parallel or acombination of both.

FIG. 16 illustrates plan views of intermediate structures at variousstages of fabricating a thin film-based energy storage device (ESD)1600D having a plurality of ESD cells or units that are electricallyconnected series, where each of the ESD units comprises laterallyadjacent current collectors and electrodes in a similar manner asdescribed above with FIGS. 2A/2B. In the illustrated embodiment, the ESD1600D includes three units or cells that are connected in electricalseries. FIG. 17 illustrates a cross-sectional view of a thin film-basedESD 1700 comprising a plurality of serially connected ESD units eachhaving laterally adjacent current collectors and electrode layers, wherethe energy storage device is fabricated according to the fabricationprocess similar to that illustrated in FIG. 16. The ESD 1700 cancorrespond to the ESD 1600D of FIG. 16 through the section 16-16′,except the ESD 1700 includes four units or cells that are connected inelectrical series.

The intermediate structure 1600A illustrates a substrate 104 on which afirst current collector 108 configured for a first polarity, a secondcurrent collector 124 configured for a second polarity opposite to thefirst polarity, and a plurality of intermediate current collectors 128are deposited or printed. The intermediate structure 1600B illustratesthe intermediate structure 1600A after a first electrode layer 112 isdeposited or printed over or on the first current collector 108 and overor on a portion of each of the intermediate current collectors 128. Theintermediate structure 1600C illustrates the intermediate structure1600B after a second electrode layer 120 is deposited or printed over oron the second current collector 124 and over or on a portion of each ofthe intermediate current collectors 128. The second electrode layer 120is formed adjacent to the first electrode 112 on each of theintermediate current collectors 128. Thus formed, the first and secondelectrode layers 112, 120 that are disposed laterally adjacent to eachother on different ones of the current collectors 108, 128, 124 areseparated by a gap therebetween, in a similar manner to the gap 210described above with respect to ESDs having laterally disposed electrodelayer arrangements (e.g., FIGS. 2A/2B). The intermediate structure 1600Dillustrates the intermediate structure 1600C after depositing orprinting a separator 116 over each of laterally adjacent pairs of thefirst and second electrode layers 112, 120. As illustrated in FIG. 17representing a cross-sectional view of the ESD 1700 that is similar tothe view of the section 16-16′ through the ESD 1600D, each pair of thefirst and second electrode layers 112, 120 disposed on electricallyseparated ones of the current collectors 108, 128, 124 and separated bya gap therebetween. The first and second electrode layers 112, 120 ofeach ESD unit or cell is formed on different ones of the currentcollectors 108, 128, 124 while being connected by a separator layer 116that fills the gap formed therebetween. Thus configured, each of thepairs of first and second electrodes 112, 120 connected by the separator116 in the horizontal direction represents a unit of ESD, and each ofthe intermediate electrodes 128 serves to electrically connect in seriesthe first and second electrodes 112, 120 of adjacent ESD units or cells.In the illustrated ESD 1600D illustrated in FIG. 16, three seriallyconnected units or cells of ESDs are formed, where the second electrodelayer 120 of the first (uppermost) ESD unit is electrically connected tothe first electrode layer 112 of the second (middle) ESD unit, and thesecond electrode layer 120 of the second (middle) ESD unit iselectrically connected to the first electrode layer 112 of the third(lower) ESD unit. The ESD 1700 (FIG. 17) may be similarly arranged withfour serially connected units or cells. However, fewer or more units orcells can be connected in series.

It will be appreciated that the multiple units or cells of ESDsdescribed above with respect to FIGS. 16 and 17 may be fabricated infour deposition steps or printing impressions that form three layerlevels, including depositing or printing the current collectors 108,124, 128, depositing or printing the first electrode layers 112,depositing or printing the second electrode layers 120 and depositing orprinting the separator 116.

It will be appreciated that, by forming serial connections betweenadjacent ESD units or cells through intermediate current collectorlayers 128, the adjacent ESD units or cells can advantageously bedirectly connected without a need for a separate wire that connects theadjacent ESD units or cells, thereby reducing the amount of electricalwiring connecting the adjacent ESD units or cells. By reducing theamount of electrical wiring and the series resistance between theadjacent ESD units or cells, the amount of excess voltage and/or energythat may be attributed to the series resistance of the electrical wiringcan in turn be reduced or eliminated.

In operation, referring to FIG. 17, when a voltage is applied betweenthe first current collector 108 and the second current collector 124 ofthe thin film-based ESD 1700, ions may be exchanged between the firstelectrode layer 112 and the second electrode layer 120 of each unit orcell of the ESD 1700 through the corresponding separator 116 formedtherebetween. Because of the lateral arrangement of the first and secondelectrode layers 112, 120, a substantial or a predominant portion of theionic exchange may occur in a lateral direction, e.g., betweenoverlapping portions of the side surfaces of the first electrode layers112 and the second electrode layers 120 across the separator-filled gaps210. Because the adjacent ESD cells or units are electrically connectedin series, the output voltages of the individual ESD cells or units arecombined as the output voltage of the resulting ESD 1700.

FIG. 18 illustrates plan views of intermediate structures at variousstages of fabricating a thin film-based energy storage device (ESD)1800D having a plurality of ESD units or cells that are electricallyconnected in series, where each of the ESD units comprises laterallyadjacent current collectors and electrode layers that have overlappingportions in the vertical direction, in a similar manner as describedabove with respect to FIG. 4. FIG. 19 illustrates a cross-sectional viewof a thin film-based ESD 1900 comprising a plurality of seriallyconnected ESD units that can correspond to the ESD 1800D illustrated inFIG. 18 through the section 18-18′. The intermediate structure 1800Aillustrates a substrate 104 on which a first current collector 108configured for a first polarity, a second current collector 124configured for a second polarity opposite to the first polarity, and aplurality of intermediate current collectors 128 are deposited orprinted. The intermediate current collectors 128 and the second currentcollector 124 are shaped as a tuning fork. The first current collector108 is disposed between “prongs” of a first intermediate currentcollector 128, the “handle” portion of the first intermediate currentcollector 128 is disposed between “prongs” of a second intermediatecurrent collector 128, and the “handle” portion of the secondintermediate current collector 128 is disposed between the “prongs” ofthe second current collector 124. The intermediate structure 1800Billustrates the intermediate structure 1800A after a first electrodelayer 112 is deposited or printed over or on the first current collector108 and over or on a portion, e.g., the “handle portion,” of each of theintermediate current collectors 128. The intermediate structure 1800Cillustrates the intermediate structure 1800B after a separator 116 isdeposited or printed over or on each of the first electrode layers 112.The intermediate structure 1800D illustrates the intermediate structure1800C after depositing or printing a second electrode layer 120 over oron each of the separators 116. As illustrated in the ESD 1900 of FIG. 19representing a cross-sectional view of the section 18-18′ through theintermediate structure 1800D in FIG. 18, each of the adjacent pairs ofthe first and second electrode layers 112, 120 formed on different onesof the current collectors 108, 128, 124 and separated in the horizontalby a gap therebetween. The adjacent ones of the first and secondelectrode layers 112, 120 that are configured as part of an ESD unit orcell are formed on different ones of the adjacent current collectors108, 128, 124 while being connected by a separator layer 116 that fillsthe gap formed therebetween. Thus configured, each of the pairs of firstand second electrode layers 112, 120 connected by a separator in thehorizontal direction represents a unit of ESD, and each of theintermediate electrodes 128 serves to electrically connect in series thefirst and second electrodes 112, 120 of adjacent ESD units or cells. Inthe illustrated ESD 1800D and ESD 1900 of FIGS. 18 and 19, respectively,three serially connected units or cells of ESDs are formed, where thesecond electrode 120 of the first (leftmost) ESD unit is electricallyconnected to the first electrode 112 of the second (middle) ESD unit,and the second electrode 120 of the second (middle ESD) unit iselectrically connected to the first electrode 112 of the third(rightmost ESD) unit. However, additional units of ESD units may beconnected in series.

It will be appreciated that the multiple units or cells of ESDsdescribed above with respect to FIGS. 18 and 19 may be fabricated infour deposition steps or printing \impressions that form three layerlevels, including depositing or printing the current collectors 108,124, 128, depositing or printing the first electrode layers 112,depositing or printing the separator 116, and depositing or printing thesecond electrode layers 120.

In operation, referring to FIG. 19, when a voltage is applied betweenthe first current collector 108 and the second current collector 124 ofthe thin film-based ESD 1900, ions may be exchanged between the firstelectrode layer 112 and the second electrode layer 120 of each unit ofESD through the corresponding separator 116. Because of the verticallyoverlapping portions of the first and second electrode layers 112, 120,a substantial or a predominant portion of the ionic exchange may occurin the vertical direction between the overlapping portions of the firstelectrode layers 112 and the second electrode layers 120. Because theadjacent ESD units or cells are electrically connected in series, theoutput voltages of the individual ESD units or cells are combined as theoutput voltage of the resulting ESD 1900.

FIG. 20 illustrates plan views of intermediate structures at variousstages of fabricating a thin film-based energy storage device (ESD)2000D having a plurality of ESD cells or units that are electricallyconnected series. Each of the cells or units comprises laterallyadjacent current collectors and electrode layers, where each of thefirst and second electrodes has a plurality of regularly spacedrectangular protrusions or fingers, where the rectangular protrusions orfingers of the first and second electrodes are interlaced or interleavedsuch that they alternate in a lateral direction. The intermediatestructure 2000A illustrates a first current collector 108 configured fora first polarity, a second current collector 124 configured for a secondpolarity opposite to the first polarity, and an intermediate currentcollector 128 formed between the first and second current collectors108, 124 that are each deposited or printed. In a similar manner asdescribed above with respect to FIG. 10C, each of the first, second andintermediate electrodes 108, 124, 128 has a strap portion and aplurality of regularly spaced rectangular protrusions or fingers, wherethe rectangular protrusions or fingers of the first and secondelectrodes alternate in a first lateral direction. The intermediatestructure 2000B illustrates the intermediate structure 2000A after afirst electrode layer 112 is deposited or printed over or on the firstcurrent collector 108 and over or on a portion of the intermediatecurrent collectors 128. The intermediate structure 2000C illustrates theintermediate structure 2000B after a second electrode layer 120 isdeposited or printed over or on the second current collector 124 andover or on a portion of the intermediate current collector 128 andadjacent to the first electrode layer 112. The first and secondelectrodes 112, 120 on the intermediate electrode 128 are physicallyseparated from each other by a gap in the second lateral orthogonal tothe first lateral direction. The intermediate structure 2000D representsthe intermediate structure 2000C after depositing or printing aseparator 116 over each of pairs of first and second electrode layers112, 120. Thus configured, each of the adjacent pairs of first andsecond electrode layers 112, 120, that are physically connected, e.g.,in the second lateral direction, represents a unit of ESD, and theintermediate electrodes 128 serves to electrically connect in series thefirst and second electrodes 112, 120 of adjacent units of ESDs. In theillustrated embodiment, two units of ESDs are formed, where the secondelectrode 120 of the first (upper) ESD unit is electrically connected tothe first electrode 112 of the second (lower) ESD unit. However,additional units of ESD units may be connected in series.

It will be appreciated that the multiple units or cells of ESD 2000D maybe fabricated in four deposition steps or printing impressions that formthree layer levels, including depositing or printing the currentcollectors 108, 124, 128, depositing or printing the first electrodelayers 112, depositing or printing the second electrode layers 120 anddepositing or printing the separator 116.

In operation, when a voltage is applied between the first currentcollector 108 and the second current collector 124 of the thinfilm-based ESD 2000D, ions may be exchanged between the first electrode112 and the second electrode 120 of each ESD cell or unit through thecorresponding separator 116, in a similar manner as described above withrespect to FIG. 17, where, the output voltages of the individual ESDunits are combined as the output voltage of the resulting ESD 2000D.

In the embodiments described above, the electrodes of the thinfilm-based ESDs comprising serially connected ESD units arealternatingly arranged in a lateral direction. However, other shapes ofthe current collectors and/or electrode layers are possible for reducingthe lateral footprint occupied by the ESD. FIG. 21 illustrates planviews and corresponding cross-sectional views of intermediate structuresat various stages of fabrication of a thin film-based energy storagedevice 2100C having laterally adjacent current collectors and electrodelayers, where each of the first and second electrodes are configured asa plurality of concentric rings or radially adjacent current collectorsand electrodes.

The intermediate structure 2100A illustrates an intermediate structureafter the current collectors are printed. Referring to the plan view(left) and a cross sectional view (right) through the section 21A-21A′,the intermediate structure 2100A includes a circular first currentcollector 108 disposed at a central region and configured for a firstpolarity. The first current collector 108 is surrounded by a circularintermediate current collector 128 concentrically surrounding the firstcurrent collector 108. The intermediate structure 2100A further includesa circular second current collector 124 concentrically surrounding theintermediate current collector 128 and configured for a second polarityopposite to the first polarity. To electrically isolate the electrodetab of the first current collector 108 while having lateral accessthereto outside the second current collector 124, a conductive lineconnecting the first current collector 108 to the correspondingelectrode tab may be formed under the first current collector 108 andthe intermediate current collector 128 and electrically isolatedtherefrom by an insulating layer (not shown) formed between theconductive line and the second and intermediate current collectors 124,128.

Still referring to FIG. 21, the intermediate structure 2100B illustratesthe intermediate structure 2100A after circular first electrode layers112 are deposited or printed over or on the first current collector 108and over or on an outer portion of the intermediate current collector128, and after circular second electrode layers 120 are deposited orprinted over or on the second current collector 108 and over or on innerportion of the intermediate current collectors 128. Referring to theplan view on the left and a corresponding cross sectional view throughthe section 21B-21B′ on the right, the first electrode layer 112 formedon the first current collector 108, the second electrode layer 120formed on the inner portion of the intermediate current collector 128,the first electrode layer 112 formed on the outer portion of theintermediate current collector 128 and the second electrode layer 120formed on the second current collector 124 are concentrically formedsuccessively in a radially outward direction. The first and secondelectrode layers 112, 120 on the intermediate electrode 128 areseparated from each other by a gap in the radial direction.

The intermediate structure 2100C illustrates the intermediate structure2100B after a separator 116 is deposited or printed over or on the firstelectrode layers 112 and over or on the second electrode layers 120, andin the gaps formed between adjacent current collectors. Thus configured,adjacent pairs of the first and second electrodes 112, 120 in the radialdirection that are physically connected by a separator therebetweenrepresents an ESD unit or cell, and the intermediate electrode 128serves to electrically connect in series the first and second electrodelayers 112, 120 of adjacent units or cells of the serially connectedESDs. In the illustrated embodiment, two units of ESDs are seriallyconnected, where the second electrode layer 120 of the first (inner) ESDunit or cell is electrically connected to the first electrode layer 112of the second (outer) ESD unit through the intermediate currentcollector 128. However, additional units of ESD units may be connectedin series.

In operation, when a voltage is applied between the first currentcollector 108 and the second current collector 124 of the thinfilm-based ESD 2100C, ions may be exchanged in a radial directionbetween the first electrode layer 112 and the second electrode layer 120of each ESD unit or cell through the corresponding separator 116, in asimilar manner as described above with respect to FIG. 17, where theoutput voltages of the individual ESD units or cells are combined as theoutput voltage of the resulting ESD 2100C.

Still referring to FIG. 21, in some embodiments, the coverage or surfaceareas of the first and second electrode layers of each of the ESD unitsor cells are about the same. In these embodiments, to keep the electrodelayers of successive ESD units to have about the same areas, the outerone of the electrode layers of each of the ESD units may be narrowerthan a corresponding inner one of the electrode layers. However,embodiments are not so limited, and coverage or surface areas of thefirst and second electrode layers of each of the ESD units or cells maybe different, e.g., to accommodate the difference in molar volumes ofthe electrode active materials, as described above with respect to,e.g., FIGS. 3A/3B.

FIG. 22 illustrates intermediate structures at various stages offabricating a thin film-based energy storage device (ESD) 2200D having aplurality of ESD units that are electrically connected series, whereeach of the ESD units comprises laterally adjacent current collectorsand electrode layers, where each of the first and second electrodes areconfigured as a plurality of concentric rings or radially adjacentcurrent collectors and electrodes, in a similar manner as describedabove with FIG. 21. Unlike the ESD 2100C illustrated in FIG. 21,however, in the illustrated embodiment in FIG. 22, the currentcollectors and the electrodes are shaped such that that the area ofoverlap between adjacent electrode of opposite polarity is enhanced forionic exchange and/or shorter charging times with a plurality ofprotrusions or fingers.

The intermediate structure 2200A illustrates an intermediate structureafter the current collectors are printed. Similar to the intermediatestructure 2100A described above with respect to FIG. 21, theintermediate structure 2200A includes a circular first current collector108 having fingers or protrusions pointing radially outward that isdisposed at a central region and configured for a first polarity. Theintermediate structure 2200B additionally includes a circularintermediate current collector 128 surrounding the first currentcollector 108 and having protrusions pointing radially inward andprotrusions pointing radially outward. The intermediate structure 2200Bfurther comprises a circular second current collector 124 surroundingthe intermediate current collector 128 having protrusions pointingradially inward and protrusions pointing radially outward and configuredfor a second polarity opposite to the first polarity. That is, while theoverall radial arrangement is similar to the intermediate structure2100A illustrated in FIG. 21C, unlike the intermediate structure 2100A,the outer perimeter of the first circular current collector 108 includesa plurality of regularly spaced radial spikes, protrusions or fingersthat radially surround a central strap portion. In addition, the innerperimeter of the intermediate current collector 128 includes a pluralityof regularly spaced radial spikes, protrusions or fingers radiallysurrounded by an outer strap portion. The protrusions, fingers or spikesof the first circular current collector 108 and the fingers or spikes ofthe intermediate current collector 128 are interlaced such that, in ananalogous manner as described above with respect to FIG. 10E, thefingers or spikes of the first circular current collector 108 and theintermediate current collector 128 are alternatingly formed at a givenradius in a circular direction. The outer perimeter of the intermediatecurrent collector 128 includes a plurality of regularly spaced radialprotrusions or corrugations and the inner perimeter of the secondcurrent collector 124 includes a plurality of regularly spaced radialprotrusions or corrugations. The protrusions or corrugations of theintermediate current collector 128 and the protrusions or corrugationsof the second current collector 124 are interlaced such that, in ananalogous manner as described above with respect to FIG. 10E, theprotrusions or corrugations of the intermediate circular currentcollector 128 and the second current collector 124 are alternatinglyformed at a given radius in a circular direction.

The intermediate structure 2200B illustrates the intermediate structure2100A after the first electrode layers 112 are deposited or printed overor on the first current collector 108 including the fingers, spikes orprotrusions and over or on an outer portion of the intermediate currentcollector 128 including the protrusions and corrugations.

The intermediate structure 2200C illustrates the intermediate structure2200B after the second electrode layers 124 are deposited or printedover or on the second current collector 124 including the protrusions orcorrugations and over or on an inner portion of the intermediate currentcollector 128 including the fingers, spikes or or protrusions of theintermediate current collector 128.

Thus formed, the inner first electrode layer 112 on the first currentcollector 108 comprises outward-pointing fingers, spikes or protrusionsand the inner second electrode 120 on the intermediate current collector128 comprises inward-pointing fingers, spikes or protrusions. Thefingers, spikes or protrusions of the first electrode layer 112 and thefingers, spikes or protrusions of the second electrode layer 120 areinterlaced with each other and are alternatingly formed at a givenradius in a circular direction. Similarly, the outer first electrodelayer 112 on the intermediate current collector 128 comprisesprotrusions or corrugations and the outer second electrode layer 120 onthe second current collector 124 comprises protrusions or corrugations.The protrusions or corrugations of the first electrode layer 112 and theprotrusions or corrugations of the adjacent second electrode layer 120are interlaced and are alternatingly formed at a given radius in acircular direction.

The intermediate structure 2200D illustrates the intermediate structure2100B after a separator 116 is deposited or printed over or on the firstelectrodes 112 and over or on the second electrodes 120, and in the gapsformed between adjacent electrodes, in a similar manner as describedabove with respect to FIG. 21. Thus configured, adjacent pairs of firstand second electrode layers 112, 120 in the radial direction that arephysically connected by a separator therebetween represents an ESC unitor cell, and the intermediate electrode 128 serves to electricallyconnect in series the first and second electrode layers 112, 120 ofadjacent units or cells of the serially connected ESDs. In theillustrated embodiment, two units of ESDs are serially connected, wherethe second electrode layer 120 of the first (inner) ESD unit iselectrically connected to the first electrode layer 112 of the second(outer) ESD unit through the intermediate current collector 128.However, additional units of ESD units may be connected in series.

In operation, when a voltage is applied between the first currentcollector 108 and the second current collector 124 of the thinfilm-based ESD 2200D, ions may be exchanged between protrusions of thefirst electrode layer 112 and the protrusions of the second electrodelayer 120 of each ESD unit or cell through the corresponding separator116, in a similar manner as described above with respect to FIG. 17,where the output voltages of the individual ESD units are combined asthe output voltage of the resulting ESD 2200D.

It will be appreciated that, in FIG. 22, the protrusions of theelectrodes and current collectors of inner and outer ESD units can haveany suitable shape, e.g., any of the shapes described above with respectto FIGS. 10C-10E, which may be particularly configured to achievedesired ion exchange enhancement effects.

It will be appreciated that an ESD having electrodes arranged as in FIG.22 can have, in addition to the increased utility advantages such asenhanced ionic exchange between electrodes of opposite types, aestheticadvantage, e.g., for wearable devices.

It will be appreciated that, as described herein, while some ESDs may bedescribed as having a particular number of ESD cells or units that areelectrically connected in series, embodiments are not so limited and anynumber of ESD units can be electrically connected in series, therebyforming an ESD having any suitably high output voltage that is a sum ofoutput voltages of the ESD cells or units therein. For example, each ESDunit may have an output voltage of 0.5V to 1.0V, 1.0V to 1.5V, 1.5V to2.0 V, 2.0V to 2.5V, 2.5V to 3.0V, 3.0V to 3.5V, 3.5V to 4.0V, 4.5V to5.0V, or a voltage in range defined by any of these values, for instance1.4-2.7V.

It will further be appreciated that, as described herein, while someESDs having serially connected ESD cells or units may have particularshapes of current collectors and/or electrodes and their arrangementsthat have been illustrated, other shapes and arrangements are possible,e.g., any polygonal shapes and linear and nonlinear arrangements tofurther increase the overlapping area between electrode layers ofopposite polarities to increase current.

Wearable Thin Film-Based Energy Storage Devices Integrated with CoreDevices

Many wearable personal electronics can benefit from an energy storagedevice (ESD) that is integrated with a core device. To be integratedwith a core device as part of a wearable device, the ESD should ideallybe flexible, light weight, customizable, wearable, skin-conforming,and/or monolithically integratable with the core device. Such ESD can besuitable, among other things, as wearable healthcare devices forapplications in fitness, medical diagnosis, prosthetics, and robotics,to name a few. Various embodiments of thin film-based or printed ESDsdescribed herein can advantageously be integrated with a core device aspart of various wearable devices.

FIG. 23 illustrates a plan view of a wearable device 2300 including acore device 2304 that is integrated with an energy storage device (ESD)1700, where the ESD 1700 has a plurality of units or cells that areconnected in electrical series. The wearable device 2300 can beconfigured as, e.g., a bracelet that can be worn around an extremity.The ESD 1700 is configured similarly as the ESD 1700 described abovewith respect to FIG. 17, the detailed description of which is omittedherein for brevity. The core device 2304 can be any suitable personaldevice, such as a healthcare or personal device, which is electricallyconnected to, e.g., the second electrode 124. To name a few examples,the core device 2304 that can be integrated with an ESD 1700 accordingto various embodiments described herein include, among other things, alight emitting device such as a light emitting diode, an active orpassive radio frequency identification device (RFIDs), a Bluetooth®device, a sensor, an infrared (IR) device such as an IR receiver,interface electronics, a Zigbee®-based device, a near-fieldcommunication (NFC)-based device, a smart band, a health monitor, and atracking device.

In some implementations, the wearable device 2300 may be pre-activated.That is, the core device 2304 and the ESD 1700 may be electricallyconnected as part of an activated circuit. In some otherimplementations, the wearable device 2300 may be configured to activatedby a user prior to use. For example, in the illustrated embodiment, apair of attachable electrodes, e.g., clip-on electrodes, may be providedsuch that the core device 2304 may be activated upon being electricallyconnected as part of a closed circuit with the ESD 1700. The latter typeof configurations can advantageously conserve the stored energy in theESD 1700 until the wearable device 2300 is ready to be used. There maybe one or more ESD units electrically connected in series in the ESD1700 to meet the specific output voltage requirement of the core device2304.

Field-Configurable Thin Film-Based Energy Storage Devices

In some applications, it may be desirable for an energy storage device(ESD) to be “field-configurable.” As described herein,field-configurability refers to a configuration in which a user cancustomize the voltage and/or capacity of the ESD prior to use. Asdescribed above, a desired operating voltage of an ESD may be attainedby connecting two or more ESD units or cells in series, where each ofthe ESD units or cells adds its voltage potential to the total terminalvoltage. On the other hand, a desired capacity may be attained byconnecting two or more ESD units or cells in parallel, where each of theESD units or cells adds its capacity to the total capacity measured inampere-hour (Ah).

FIG. 24 illustrates a plan view of a field-configurable thin film-basedenergy storage device (ESD) 2400 having an array of ESD units or cellsthat are formed on a substrate having perforations such that a desirednumber of units or cells can be connected in electrical series orparallel for customizable voltage and/or capacity. The ESD 2400comprises a substrate 104 in the form of a sheet of insulating material.The substrate 104 comprises a plurality of horizontal rows ofperforations 2404 and a plurality of vertical columns of perforations2408. The lines of perforations divide the substrate 104 into an arrayof unit substrates formed by the plurality of rows of horizontalperforations 2404 and the plurality of columns by vertical perforations2408. The perforations are configured such that a user can tear alongany desired path to define a contiguous substrate having a desirednumber of unit substrates each having an ESD unit or cell formedthereon.

Still referring to FIG. 24, an ESD cell or unit similar to the ESD 400described above with respect to FIG. 4 is formed in each of the unitsubstrates, such that the ESD 2400 comprises an array of ESD cells orunits comprising one or more rows of ESD cells or units and one or morecolumns of ESD cells or units. Each row of the ESD 2400 comprises aplurality of ESD units comprising a first current collector 108, asecond current collector 124 and one or more intermediate currentcollectors 128 that are configured as described above with respect tothe ESD 1900 in FIG. 19, the detailed description of which is omittedherein for brevity. In addition, the first current collectors 108 of theESD units in each of the columns are connected to each other, theintermediate collectors 128 of the ESD units in each of the columns areconnected to each other, and the second current collectors 124 of theESD units in each of the columns are connected to each other. Asconfigured, the ESD cell or units in a given row are electricallyconnected in series, and the ESD cells or units in a given column areelectrically connected in parallel.

In use, any desired pattern of ESD cells or units can be formed bytearing along the perforations that outline the desired pattern, suchthat the ESD units are electrically connected in a combination ofelectrical series and/or parallel to provide a customized capacity andoutput voltage. When the pattern of ESD units are formed by tearingalong the perforations, the overlying current collectors may separate bybrittle fracture.

While in the illustrated embodiment, the horizontal perforations 2404and vertical perforations 2408 facilitate the separation of the ESDunits, embodiments are not so limited. In other embodiments theseparation of the ESD units may be facilitated by grooves, notches,thinned regions, impressions, etc. In yet other embodiments, the ESDunits may be separated simply by hand or by using cutting devices suchas scissors or knives.

Thin Film-Based Energy Storage Devices Integrated with Thin Film-BasedCore Devices

Various thin film-based energy storage devices (ESDs) described hereinmay be integrated with various thin film-based core devices powered bythe ESD, thereby forming an integrated thin film-based electronic devicecomprising a thin film-based core device and a thin film-based ESD.Efficient integration may be achieved in part because similar materialsmay be used to print different components of the ESD and the thinfilm-based core device powered by the thin film-based ESD. At least somelayers of the thin film-based ESD can be printed on, e.g., directly on,the thin film-based core device powered by the thin film-based ESD,which may in turn be partly or entirely formed of printed components orlayers. In some implementations, substantially the entire integratedthin film-based electronic device including the thin film-based ESD andthe thin film-based core device can be fabricated by printing.

An integrated thin film-based electronic device including a thinfilm-based ESD and an integrated thin film-based core device powered bythe ESD can have various advantages. For example, the operationalcurrent and/or voltage of the ESD can be customized as described aboveto meet the operational power and energy needs of the integrated thinfilm-based core device. In addition, the integrated thin film-basedelectronic device can enable reduction in the overall thickness and/orfootprint of the combination of the thin film-based ESD and the thinfilm-based core device. In addition, the integrated thin film-basedelectronic device can enable reduction in the overall number ofmanufacturing process steps.

In various embodiments described below, the thin film-based ESD can beintegrated with the thin film-based core device powered by the ESD byforming at least one layer of the ESD on, e.g., directly on, the thinfilm-based core device powered by the ESD. Alternatively, at least onelayer of the thin film-based core device powered by the ESD can beformed on, e.g., directly on, the thin film-based ESD. For example, atleast one layer of the ESD may be printed on, e.g., directly printed on,the thin film-based core device powered by the ESD. Alternatively, atleast one layer of the thin film-based core device powered by the ESDmay be printed on, e.g., directly printed on, the thin film-based ESD.By having at least one layer of one of the thin film-based ESD or thethin film-based core device formed or printed on the other of the thinfilm-based ESD or the thin film-based core device, the two devices canbe disposed at relative positions that may provide various advantages.For example, by directly printing at least one layer of one of the thinfilm-based ESD or the thin film-based core device on the other of thethin film-based ESD or the thin film-based core device, the amount ofelectrical wiring connecting the two devices can be reduced. By reducingthe amount of electrical wiring and the series resistance between thethin film-based ESD and the thin film-based core device powered by theESD, the amount of excess voltage and/or energy that may be attributedto the series resistance of the electrical wiring can in turn be reducedor eliminated.

FIG. 25 illustrates a side view of an integrated thin film-basedelectronic device 2500 according to some embodiments, having integratedtherein a thin film-based energy storage device (ESD) having laterallyadjacent current collectors and electrode layers, and a thin film-basedcore device having laterally arranged electrical terminals and poweredby the thin film-based ESD.

The integrated thin film-based electronic device 2500 includes a thinfilm-based core device 2504 formed on a substrate 104. The thinfilm-based core device 2504 has formed thereon first and secondterminals 2508, 2512 that are configured to receive power and energyfrom the thin film-based ESD. The first and second terminals 2508, 2512are formed laterally adjacent to each other and over or on the thinfilm-based core device 2504. One or more components or layers of thethin film-based core device 2504 including the first and secondterminals 2508, 2512 can be printed using a suitable printing processdescribed herein.

The thin film-based core device 2504 can be any suitable device suitablefor integration with a thin film-based ESD, such as a healthcare orpersonal device. To name a few examples, the thin film-based core device2504 can include, among other things, a light emitting device such as alight emitting diode, an acoustic device, a monitor device, a motordevice, a movement device, a display device, an antenna, an active orpassive radio frequency identification device (RFIDs), a Bluetooth®device, a sensor, an infrared (IR) device such as an IR receiver,interface electronics, a Zigbee®-based device, a A-wave device, anear-field communication (NFC)-based device, a smart band, a healthmonitor, a fitness tracking device, a smart watch, a position-trackingdevice such as a GPS-tracking device, a low power wireless personal areanetwork (LoWPAN) device, and a low power wide area network (LPWAN)device a to name a few examples.

The first terminal 2508 can be, e.g., one of a positive or a negativepower terminal, and the second terminal 2512 can be, e.g., the other ofthe positive or the negative power terminal. The first and secondterminals 2508, 2512 are configured to receive power therethrough toprovide the power and energy to the thin film-based core device 2504.

Still referring to FIG. 25, the integrated thin film-based electronicdevice 2500 additionally includes an integrated thin film-based ESDformed over the thin film-based core device 2504. The thin-film basedESD is positioned such that at least a portion thereof laterallyoverlaps the underlying thin film-based core device 2504. The thinfilm-based ESD is similar to the thin film-based ESD 200 illustratedwith respect to FIGS. 2A and 2B. The integrated thin film-based ESDincludes a first current collector 108, a second current collector 124,a first electrode layer 112, a second electrode layer 120 and aseparator 116, and the detailed description of corresponding features isomitted herein for brevity.

In the integrated thin film-based electronic device 2500, the first andsecond current collectors 108, 124 are electrically connected to thefirst and second terminals 2508, 2512, respectively. In the illustratedembodiment, advantageously, because the thin film-based ESD is formedover to overlap the underlying thin film-based core device 2504, thefirst and second current collectors 108, 124 can be formed on ordirectly on, e.g., directly printed on, the first and second terminals2508, 2512, respectively. It will be appreciated that, when the firstand the second terminals 2508, 2512 are formed directly on the first andsecond current collectors 108, 124 respectively as illustrated, one ormore intervening conductive elements such as wires can be omitted,thereby reducing excess voltage or energy dissipated by the interveningconductive elements. However, embodiments are not so limited and in someother embodiments, there may be intervening conductive elements, e.g.,printed conductive structures, between the first current collector 108and the first terminal 2508, and/or between the second current collector120 and the second terminal 2512. Because the thin film-based ESD ispositioned relatively in close proximity to the thin film-based coredevice 2504, the amount of electrical series resistance resultingtherefrom is reduced or minimized.

FIG. 26 illustrates a side view of a thin film-based energy storagedevice 2600 according to some embodiments, having integrated therein athin film-based energy storage device (ESD) having laterally adjacentcurrent collectors and electrode layers, and a thin film-based coredevice having vertically arranged electrical terminals and powered bythe thin film-based ESD. Similar to the device illustrated with respectto FIG. 25, the integrated thin film-based electronic device 2600includes a thin film-based core device 2504 formed on a substrate 104and an integrated thin film-based ESD. The features of integrated thinfilm-based electronic device 2600 that correspond to or are analogous tothose of the integrated thin film-based electronic device 2500 (FIG. 25)are omitted herein for brevity.

The thin film-based core device 2504 has formed thereon first and secondterminals 2508, 2512 and is configured to receive power and energy fromthe thin film-based ESD. However, unlike the thin film-based core deviceillustrated with respect to FIG. 25, the first and second terminals2508, 2512 of the thin film-based core device 2504 are disposed onopposing surfaces of the thin film-based core device 2504 in thevertical direction. The first terminal 2508 is formed on the top surfaceof the thin film-based core device 2504 and does not extend outsidethereof, while the second terminal 2512 is formed on the bottom surfaceof the thin film-based core device 2504 and extends beyond the bottomsurface thereof.

Still referring to FIG. 26, the integrated thin film-based electronicdevice 2600 additionally includes an integrated thin film-based ESDformed over the thin film-based core device 2504. Similar to thatdescribed above with respect to FIG. 25, the thin film-based ESD ispositioned such that at least a portion thereof laterally overlaps theunderlying thin film-based core device 2504. The integrated thinfilm-based ESD includes a first current collector 108, a second currentcollector 124, a first electrode layer 112, a second electrode layer 120and a separator 116. The thin film-based core device 2504 is disposedbetween the first current collector 108 and the substrate 104, suchthat, while the first current collector 108 and the first electrodelayer 112 overlap the thin film-based core device 2504, the secondcurrent collector 124 and the second electrode layer 120 are formed onthe portion of the second terminal 2512 that extends beyond the bottomsurface of the thin film-based core device 2504, and do not overlap thethin film-based core device 2504.

FIG. 27 illustrates a side view of a thin film-based energy storagedevice 2700 according to some embodiments, having integrated therein athin film-based ESD having vertically stacked current collectors andelectrode layers, and a thin film-based core device having verticallyarranged electrical terminals and powered by the thin film-based ESD.

Similar to the device illustrated with respect to FIGS. 25 and 26, theintegrated thin film-based electronic device 2700 includes a thinfilm-based core device 2504 formed on a substrate 104 and an integratedthin film-based ESD. The features of integrated thin film-basedelectronic device 2700 that are similar or analogous to those of theintegrated thin film-based electronic devices 2500, 2600 (FIGS. 25, 26)are omitted herein for brevity.

The thin film-based core device 2504 has formed thereon first and secondterminals 2508, 2512 and is configured to receive power and energy fromthe thin film-based ESD. Similar to the thin film-based core deviceillustrated with respect to FIG. 26, the first and second terminals2508, 2512 of the thin film-based core device 2504 are disposed onopposing surfaces of thin film-based core device 2504 in the verticaldirection. The first terminal 2508 is formed on the bottom surface ofthe thin film-based core device 2504, and the second terminal 2512 isformed on the top surface of the thin film-based core device 2504.

Still referring to FIG. 27, similar to the devices described above withrespect to FIGS. 25 and 26, the thin film-based ESD is positioned suchthat at least a portion thereof laterally overlaps the thin film-basedcore device 2504. However, unlike the integrated thin film-based ESDshaving laterally adjacent current collectors and electrodes describedabove with respect to FIGS. 25 and 26, the thin film-based ESD of theintegrated thin film-based electronic device 2700 has vertically stackedcurrent collectors and electrode layers, in a similar manner asdescribed above with respect to FIG. 1. The ESD includes a substrate 104on which a stack of layers is formed. The stack of layers includes afirst current collector 108 of a first type formed over or on thesubstrate 104, a first electrode layer 112 of a first type formed overor on the first current collector 108, a separator 116 formed over or onthe first electrode 112, a second electrode layer 120 of a second typeformed over or on the separator 116 and a second current collector 124of a second type formed over or on the second electrode layer 120. Thefirst current collector 108 laterally extends outside and beyond thefirst electrode layer 112, and the first terminal 2508 of the thinfilm-based core device 2504 is formed to overlap, on or in contacttherewith. Similarly, the second current collector 124 laterally extendsoutside and beyond the second electrode layer 120, and the secondterminal 2512 of the thin film-based core device 2504 is formed tooverlap, on or in contact therewith. Thus configured, the stackincluding the first electrode layer 112, the separator 116 and thesecond electrode layer 120 is formed adjacent to the stack including thefirst terminal 2508, the thin film-based core device 2504 and the secondterminal 2512, where both stacks are vertically interposed between thefirst and second current collectors 108, 124.

FIG. 28 illustrates a thin film-based light-emitting device 2800 havingvertically arranged electrical terminals and configured to be powered byvarious thin film-based energy storage devices described herein. FIG. 29illustrates a side view of an integrated thin film-based electronicdevice 2900 having integrated therein a thin film-based ESD havinglaterally adjacent current collectors and electrode layers, and the thinfilm-based light-emitting device illustrated with respect to FIG. 28having vertically arranged electrical terminals and powered by the thinfilm-based ESD. Similar to the device illustrated with respect to FIG.26, the integrated thin film-based electronic device 2900 includes athin film-based electronic device that is a thin film-based lightemitting device 2800, and an integrated thin film-based ESD. Thefeatures of integrated thin film-based electronic device 2900 that aresimilar or analogous to those of the integrated thin film-basedelectronic device 2600 (FIG. 26) are omitted herein for brevity.

Referring to FIG. 28, the thin film-based light-emitting device 2800 maybe formed over or on the substrate 104, which can be a transparent glassor polymeric substrate, e.g., a PET substrate. The light-emitting device2800 comprises a light-emitting layer 2804, which can include one ormore light emitting elements, such as light emitting diodes (LEDs). Thelight-emitting device 2800 has formed thereon or thereover first andsecond terminals 2508, 2512 that are configured for receiving power andenergy from the thin film-based ESD. The first and second terminals2508, 2512 may be disposed on opposing surfaces of the light-emittinglayer 2804 in the vertical direction. The first terminal 2508 is formedon the top surface of the light-emitting layer 2804 and does not extendoutside thereof, while the second terminal 2512 is formed on the bottomsurface of the light-emitting layer 2804 and extends beyond the bottomsurface thereof.

In some embodiments, the light-emitting device 2800 is configured toemit light (hν) through the transparent substrate 104. In theseembodiments, the second terminal 2512 comprises a transparent conductor.The transparent conductor can include, e.g., indium tin oxide (ITO) or athin film comprising silver, e.g., a silver nanowire-based coating. Thefirst terminal 2508 may be formed of any printable conductive materialdescribed herein, e.g., conductive silver. In the illustratedembodiment, an additional conductive layer 2812 may be formed on thesecond terminal 2512 to provide mechanical stability, additionalelectrical conductivity or both.

In some embodiments, the light emitting device 2800 may be encapsulated,e.g., hermetically sealed, in an insulator layer or a passivating layer2808 such as an oxide, a nitride or a polymer layer configured toprovide protection to the light-emitting layer 2804 from harmful effectsof the environment such as moisture or air. In these embodiments, whilenot shown, an electrical connection may be formed through the insulatorlayer 2808 between the first terminal 2508 and the light-emitting layer2804.

Referring to FIG. 29, the integrated thin film-based electronic device2900 additionally includes at least a portion of an integrated thinfilm-based ESD formed over the thin film-based light emitting device2800. Similar to the device described above with respect to FIG. 26, thethin film-based ESD is positioned such that at least a portion thereoflaterally overlaps the thin film-based light emitting device 2800. Theintegrated thin film-based ESD includes a first current collector 108, asecond current collector 124, a first electrode layer 112, a secondelectrode layer 120 and a separator 116. The thin film-based lightemitting device 2800 is disposed between the first current collector 108and the substrate 104, such that the first current collector 108 and thefirst electrode layer 112 overlap the thin film-based light-emittingdevice 2800, and the second current collector 124 and the secondelectrode layer 120 are formed on the portion of the second terminal2512 that extends beyond the bottom surface of the thin film-basedlight-emitting device 2504 or on the additional conductive layer 2812when present.

FIG. 30 illustrates a top down view of an integrated thin film-basedelectronic device 3000 having integrated therein a thin film-based ESDincluding a plurality of units or cells that are connected in electricalseries, and a thin film-based core device such as a light-emittingdevice 2800 illustrated with respect to FIG. 28 having verticallyarranged electrical terminals and powered by the thin film-based ESD.The thin film-based light emitting device 2800 is configured andintegrated in a similar manner as described above with respect to theintegrated thin film-based electronic device 2900 described above withrespect to FIG. 29, and a detailed description of corresponding orsimilar features is omitted herein for brevity. Unlike the thin-filmbased electronic device 2900 (FIG. 29), however, the integrated thinfilm-based ESD includes a plurality of units or cells. The plurality ofunits or cells are serially connected in a manner similar to thatdescribed above with respect to FIGS. 16 and 17, where each of the ESDunits or cells comprises laterally adjacent current collectors andelectrodes in a similar manner as described above with FIGS. 2A/2B. Adetailed description of corresponding features similar to those of FIGS.2A/2B and 16 and 17 are omitted herein for brevity. Thus configured, theintegrated thin film-based ESD comprises pairs of first and secondelectrodes 112, 120 physically connected by a separator 116, where eachpair represents a unit or cell of the thin film-based ESD. Each of theintermediate current collectors 128 serves to electrically connect inseries the first and second electrodes 112, 120 of adjacent ESD units orcells. In the illustrated integrated thin-film based ESD, three seriallyconnected units or cells of ESDs are formed, where the second electrodelayer 120 of the first (lowermost) ESD unit is electrically connected tothe first electrode layer 112 of the second (upper left) ESD unit by thefirst (left) intermediate current collector 128, and the secondelectrode layer 120 of the second (upper left) ESD unit is electricallyconnected to the first electrode layer 112 of the third (upper right)ESD unit by the second (right) intermediate current collector 128.

Still referring to FIG. 30, the thin film-based light emitting device2800 is integrated in a similar manner as described above with respectto FIG. 29, in which the first terminal 2508 is electrically connectedto and disposed underneath the first current collector 108 of the first(lowermost) ESD unit. The second terminal 2512, which may betransparent, and optionally the additional conductive layer 2812 whenpresent, are electrically connected and disposed underneath the secondcurrent collector 124 of the third (upper right) ESD unit. The lightemitting layer 2804 is electrically connected to and formed underneaththe first terminal 2508. In a similar manner as described above withrespect to FIG. 29, the second terminal 2512 may be formed on a bottomsurface of the light emitting layer 2804 and laterally extend toelectrically connect to the second current collector 124 of the third(upper right) ESD unit, e.g., through the additional conductive layer2812 when present. While not illustrated, at least the thin film-basedlight emitting device 2800 may be formed over or on a transparentsubstrate, such that light may be transmitted therethrough, as describedabove with respect to FIG. 29.

Still referring to FIG. 30, in some embodiments, the integrated thinfilm-based electronic device 3000 further comprises a switch 3004, whichmay be configured to electrically activate the circuit of the integratedthin film-based electronic device 3000 upon being engaged or activated.The switch 3004 may be engaged in any suitable manner, e.g., upon beingmechanically pressed. In some embodiments, the switch 3004 may be aone-time switch. For example, the switch 3004 may be configured as abutton including a conductive fluid or a deformable material thatelectrically connects or shorts portions of one of the intermediatecurrent collectors 128 that may be initially electrically separated. Inthe illustrated embodiment, the first (left) intermediate currentcollector 128 may initially be electrically separated into (upper andlower) portions, which may be electrically shorted upon activation ofthe switch 3004, e.g., by mechanically pressing the button. However,embodiments are not so limited, and the switch 3004 may be activated byany other suitable mechanisms, e.g., resistance change orphoto-activation.

FIG. 31 illustrates a top down optical micrograph of an actuallyfabricated integrated thin film-based electronic device 3100 havingintegrated therein a thin film-based energy storage device including aplurality of units or cells that are connected in electrical series.Each of the electrodes of each unit or cell have a plurality ofregularly spaced elongated protrusions or fingers. The integrated thinfilm-based electronic device 3100 additionally has integrated therein athin film-based light-emitting device similar to that described abovewith respect to FIG. 28, having vertically arranged electrical terminalsand powered by the thin film-based ESD. The integrated thin film-basedelectronic device 3100 is configured and integrated in a similar manneras described above with respect to the integrated thin film-basedelectronic device 3000 (FIG. 30), and a detailed description ofcorresponding or similar features is omitted herein for brevity. Similarto the thin-film based electronic device 3000 (FIG. 3000), the thin-filmbased electronic device 3100 comprises an integrated thin film-based ESDincluding a plurality of units or cells that are serially connected.However, in the integrated thin film-based electronic device 3100, in asimilar manner as described above with respect to FIG. 10E, each unitcell comprises first and second electrode layers 112, 120 that have astrap portion and a plurality of regularly spaced protrusions, fingers,tines or spikes, where the elongated protrusions, fingers, tines orspikes of the first and second electrode layers 112, 120 are interlacedor interleaved such that they alternate in a lateral direction, therebyhaving increased overlapping edge lengths of the first and secondelectrodes layers 112, 120. Thus configured, the integrated thinfilm-based ESD comprises pairs of first and second electrode layers 112,120 connected by a separator 116, where each pair represents a unit ofESD. Each of the intermediate electrodes 128 serves to electricallyconnect in series the first and second electrodes 112, 120 of adjacentESD units or cells. In the illustrated integrated thin-film based ESD,three serially connected units or cells of ESDs are formed, where thesecond electrode layer 120 of the first (upper left) ESD unit iselectrically connected to the first electrode layer 112 of the second(upper right) ESD unit, and the second electrode layer 120 of the second(upper right) ESD unit is electrically connected to the first electrodelayer 112 of the third (bottom right) ESD unit.

Still referring to FIG. 31, the thin film-based light emitting device2800 is integrated in a similar manner as described above with respectto FIG. 30, and a detailed description of corresponding features isomitted herein for brevity. The first terminal is electrically connectedto and disposed underneath the first intermediate current collector 128of the first (upper right) ESD unit and the second terminal, which maybe transparent, and optionally the additional conductive layer whenpresent, are electrically connected and disposed underneath the secondintermediate current collector 128 of the second (upper right) ESD unit.A least the thin film-based light emitting device 2800 may be formedover or on a transparent substrate, such that light may be transmittedtherethrough. In the illustrated embodiment, the first current collector108 of the first (upper left) ESD unit has been electrically shorted tothe second current collector 124 of the third (bottom right) ESD unitupon activation of the switch 3004.

It will be appreciated that, while in each of the integrated thinfilm-based electronic devices described above with respect to FIGS.25-31, first and second current collectors of a thin film-based ESD arerespectively electrically connected to first and second terminals of thea thin film-based core device, where the first current collector and thefirst terminal are separate layers and the second current collector andthe second terminal are discrete layers, embodiments are not so limited.In some other embodiments, the first current collector of the thinfilm-based ESD and the first terminal of the thin film-based core devicecan be formed as an integrated single thin film layer. Similarly, thesecond current collector of the thin film-based ESD and the secondterminal of the thin film-based core device can be formed as anintegrated single thin film layer. That is, the direct formation of thethin film-based ESD and the thin film-based core device on one anothercan allow for one or the other of the first current collector and thefirst terminal to be omitted, and/or one or the other of the secondcurrent collector and the second terminal to be omitted.

Rechargeable Thin Film-Based Energy Storage Devices Integrated withEnergy Harvesting Devices

Various thin film-based energy storage devices (ESDs) described hereinmay be integrated with thin film-based energy harvesting devices,thereby forming an integrated rechargeable thin film-based ESDs. Similarto various thin film-based core devices integrated with the thinfilm-based ESDs described above, similar materials and methods may beused to print components of the thin film-based ESD as well as the thinfilm-based energy harvesting devices configured to charge or rechargethe thin film-based ESDs. At least some layers of the thin film-basedenergy harvesting device can be formed on or printed on, e.g., directlyformed or printed on, the thin film-based ESD or vice versa. In someimplementations, substantially the entire integrated electronic deviceincluding the thin film-based ESD and the thin film-based energyharvesting device can be fabricated by printing.

In various embodiments described below, the thin film-based ESD can beintegrated with the thin film-based energy harvesting device configuredto charge/recharge the thin film-based ESD by forming or printing atleast one layer of the ESD, e.g., forming or printing directly on, thethin film-based energy harvesting device. Alternatively, at least onelayer of the thin film-based energy harvesting device can be formed orprinted on, e.g., directly formed or printed on, the thin film-basedESD. By having at least one layer of one of the thin film-based ESD orthe thin film-based energy harvesting device formed or printed on theother of the thin film-based ESD or the thin film-based energyharvesting device, the two devices can be disposed at relative positionsthat may provide various advantages. For example, by directly printingat least one layer of one of the thin film-based ESD or the thinfilm-based energy harvesting device on the other of the thin film-basedESD or the thin film-based energy harvesting device, the amount ofelectrical wiring connecting the two devices can be reduced. By reducingthe amount of electrical wiring and the series resistance between thethin film-based ESD and the thin film-based energy harvesting device,the amount of excess voltage and/or energy that may be dissipated by theseries resistance of the electrical wiring can in turn be reduced oreliminated.

As described herein, energy harvesting can involve converting anon-electrical form of energy into an electrical form of energy, such ascharge or voltage. A thin film-based energy harvesting device can be anysuitable device configured to harvest energy from the environment, e.g.,a photovoltaic device, a thermoelectric device, a piezoelectric device,a wireless charging device, a tribological harvesting device, anRF-based energy harvesting device, a pyroelectric energy harvestingdevice, a capacitive energy harvesting device, a microbial energyharvesting device and magnetorestrictive energy harvesting device, toname a few. The thin film-based energy harvesting device can beconfigured to partially or fully supply the power to charge or rechargethe thin film-based ESD, such that the thin-film based ESD can in turnsupply energy and power to a core device connected thereto or integratedtherein for an extended period of time without connecting a separatepower supply.

FIGS. 32 and 33 illustrate side views of an integrated thin film-basedelectronic device 3200A/3200B having integrated therein a thinfilm-based energy storage device (ESD) having laterally adjacent currentcollectors and electrode layers, and a thin film-based energy harvestingdevice configured to charge/recharge the thin film-based ESD. FIG. 32illustrates the integrated thin film-based electronic device 3200A inwhich the integrated ESD is in a charging mode, while FIG. 33illustrates the integrated thin film-based electronic device 3200B inwhich the integrated ESD is in a discharging mode.

The integrated thin film-based electronic device 3200A/3200B includes anintegrated thin film-based ESD formed over or on a substrate (not shownfor clarity). The thin film-based ESD includes a first current collector108 and a second current collector 124 that are laterally adjacentlydisposed, and a first electrode layer 112 and second electrode layer 120that are laterally adjacently disposed. In a similar manner as describedabove with respect to, e.g., the ESD illustrated in FIGS. 2A/2B, thefirst electrode layer 112 and the second electrode layer 120 are formedon or over the first current collector 108 and the second currentcollector 124, respectively. A separator 116 is disposed in a gapseparating the first and second current collectors 108, 124, and in agap separating the first and second electrode layers 112, 120. Adetailed description of similar corresponding features that have beendescribed above is omitted herein for brevity. Unlike the ESD describedabove with respect to FIGS. 2A/2B, however, while the separator 116 isformed in the gap formed between the first and second electrode layers112, 120, it is not formed over the first and second electrode layers112, 120.

The first and second electrode layers 112, 120 can include any suitablepair of active materials described above, e.g., Ag/ZnO pair or Mn/ZnOpair.

Still referring to FIGS. 32 and 33, the integrated thin film-basedelectronic device 3200A/3200B has formed over or on the thin film-basedESD one or more thin film-based energy harvesting devices. The one ormore thin-film based energy harvesting devices are positioned such thatat least a portion thereof laterally overlaps the underlying thinfilm-based ESD. In the illustrated example configuration, a first thinfilm-based energy harvesting device 3204A is formed over or on the firstelectrode layer 112 and vertically disposed between the first electrodelayer 112 and a first conductive layer 3220A. The first conductive layer3220A may be transparent when the underlying thin film-based energyharvesting device includes a photovoltaic device. A second thinfilm-based energy harvesting device 3204B is formed over or on thesecond electrode layer 120 and vertically disposed between the secondelectrode layer 120 and a second conductive layer 3220B. The secondconductive layer 3220B may be transparent when the underlying thinfilm-based energy harvesting device includes a photovoltaic device.

In the illustrated example, each of the first and second thin film-basedenergy harvesting devices 3204A, 3204B is a photovoltaic device, e.g., asolar cell. The first thin film-based energy harvesting device 3204Aincludes a first photovoltaic layer 3208A, which may include a firstactive or absorber material or a first heterojunction or a PN junctionformed by a p-type semiconductor material and an n-type semiconductormaterial, and which may be formed between a first electron transportlayer 3216A and a first hole transport layer 3212A. Similarly, thesecond thin film-based energy harvesting device 3204B includes a secondphotovoltaic layer 3208B, which may include a second active or absorbermaterial or a second heterojunction or a PN junction formed by a p-typesemiconductor material and an n-type semiconductor material, and whichmay be formed between a second electron transport layer 3216B and asecond hole transport layer 3212B. The first and second thin film-basedenergy harvesting devices 3204A and 3204B may be physically separated bythe separator 116 or an insulating layer 3228, while being electricallyconnected in series. The serial connection may be formed by, e.g., adiode 3224 electrically connecting the first and second conductivelayers 3220A and 3220B. The series diode 3224 may be configured to beunder a forward bias when the first and second thin film-based energyharvesting devices 3204A, 3204B are in a charging mode, and under areverse bias when the first and second thin film-based energy harvestingdevise 3204A, 3204B are in a discharging mode.

Referring to FIG. 32, in operation in the charging mode, photons (hν)absorbed by each of the first and second photovoltaic layers 3208A,3208B can generate excitons therein, which are separated into electronsand holes, or electron and hole pairs directly. The electrons travelthough the first and second electron transport layers 3216A, 3216B, andthe holes travel through the first and second hold transport layers3212A, 3212B. The electrons from the first electron transport layer3216A are collected by the first conductive layer 3220A, and theelectrons from the second electron transport layer are collected by thesecond electrode layer 120. Conversely, the holes from the first holetransport layer 3212A are collected by the first electrode layer 112,and the holes from the second hole transport layer are collected by thesecond conductive layer 3220B. The overall direction of electron flowfrom the first electrode layer 112, through the first photovoltaic layer3208A, the first conductive layer 322A, the diode 3224, which may beforward-biased, the second conductive layer 3220B and the secondphotovoltaic layer 3220B, to the second electrode layer 120 is indicatedby small arrows. The corresponding ionic transport between the first andsecond electrode layers 112, 120, through the separator 116 is indicatedby large arrows.

Referring to FIG. 33, in operation in discharge mode, the thinfilm-based energy harvesting device may be inactive, and the charge isdissipated by a load device or a core device, e.g., any of the thinfilm-based core devices described above that is connected to the firstand second current collectors 108, 124 of the thin film-based ESD andpowered by the thin film-based ESD. The direction of electron flow isindicated by small arrows and the ionic flow is indicated by largearrows. The diode 3224 may be advantageously reversely biased toeffectively block dark current, thereby improving the efficiency of thethin film-based ESD.

It will be appreciated that the first and second energy harvestingdevices 3204A, 3204B may be any suitable thin film-based photovoltaicdevice. At least one layer the energy harvesting devices 3204A, 3204Bmay be printed. For example, printable photovoltaic layers 3208A, 3208Binclude an organic polymer, an inorganic chalcogenide, or a perovskitematerial.

Examples of the photovoltaic layers 3208A, 3208B include an organicpolymer such as, e.g., poly[2-methoxy-5-(20-ethylhexyloxy)-p-phenylenevinylene] (MEH+PPV), poly(3-hexylthiophene-2,5-diyl) (P3HT),poly(N-alkyl-2,7-carbazole) (PCDTBT),poly[(4,4-bis(2-ethylhexyl)-cyclopenta-[2,1-b;3,4-b′]dithiophene)-2,6-diylalt-2,1,3-benzothiadiazole-4,7-diyl](PCPDTBT),poly[(4,4′-bis(2-ethylhexyl)dithieno[3,2-b:20,30-d]silole)-2,6-diyl-alt-(2,1,3-benzothiadiazole)-4,7-diyl](PSBTBT),poly[(2,5-bis(2-hexyldecyloxy)phenylene)-alt-(5,6-difuoro-4,7-di(thiophen-2-yl)benzo[c]-[1,2,5]thiadiazole)](PPDT2FBT),poly[(5,6-difluoro-2,1,3-benzothiadiazol-4,7-diyl)-alt-(3,3000-di(2-octyldodecyl)-2,20;50,20′;50′,20″-quaterthiophen-5,50″-diyl)](PffBT4T-2OD), or a combination thereof, to name a few.

Examples of the photovoltaic layers 3208A, 3208B include an inorganicchalcogenide such as, e.g., copper indium gallium selenides (CIGS),copper zinc tin sulfide (CZTS), copper zinc tin selenide (CZTSe) or analloy or a combination thereof, to name a few.

Examples of the photovoltaic layers 3208A, 3208B include a perovskitematerial. The perovskite material can include one or both of an organicmaterial and an inorganic material. Some perovskite materials include anorganic-inorganic hybrid material having the perovskite crystalstructure. The perovskite crystal structure can be described as ABX₃,where A is an organic (or inorganic) cation (e.g., methylammonium (MA⁺),formamidinium (FA⁺), Cs⁺, etc.), B is a metal cation (e.g., Pb₂₊, Sn²⁺,etc.), and X is an anion (e.g., I⁻, Br—, Cl⁻, SCN⁻, etc.). Theperovskite material may include, e.g., MAPbI₃ (α phase, tetragonalstructure), MAPbI₃ (β phase, tetragonal structure), MAPbI₃ (γphase,orthorhombic structure), MAPbCl₃ (α phase, cubic structure), MAPbCl₃ (βphase, tetragonal structure), MAPbCl₃ (γ phase, orthorhombic structure),MAPbBr₃ (α phase, cubic structure), MAPbBr₃ (β phase, tetragonalstructure), MAPbBr₃ (γ phase, tetragonal structure), MAPbBr₃ (δ phase,orthorhombic structure), MASnI₃ (α phase, tetragonal structure), MASnI₃(β phase, tetragonal structure), FAPbI₃ (α phase, trigonal phase),FAPbI₃ (β phase, trigonal structure), FASnI₃ (α phase, orthorhombicstructure), FASnI₃ (β phase, orthorhombic structure) or a combinationthereof, to name a few.

The first and second electron transport layers 3216A, 3216B areconfigured to have good electron transport property, and when the lightis collected through them, the first and second electron transportlayers 3216A, 3216B are transparent to the solar radiation. Examples ofmaterials that can be used include ZnO, TiO_(x), Cs₂CO₃, Nb₂O₅, andother suitable metal oxides or polymeric materials, to name a few.

The first and second hole transport layers 3212A, 3212B are configuredto have good hole transport property, and when the light is collectedthrough them, first and second hole transport layers 3212A, 3212B aretransparent to the solar radiation. Examples of materials that can beused include polymers, e.g., PEDOT:PSS, or metal oxides, e.g., MoO₃,V₂O₅, WO₃ and NiO, to name a few.

Still referring to FIGS. 32 and 33, advantageously, because the firstand second thin film-based energy harvesting devices 3204A, 3204B areformed over, on or directly on to overlap the underlying thin film-basedESD, the resulting integrated thin film-based electronic device3200A/3200B can be vertically and horizontally compact. Furthermore,when the first and second thin film-based energy harvesting devices3204A, 3204B are formed directly on the first and second currentelectrode layers 112, 120, respectively, one or more interveningconductive elements such as wires can be omitted to reduce theassociated series resistance, thereby reducing excess voltage or energydissipated by the intervening conductive elements. However, embodimentsare not so limited and in other embodiments, there may be interveningconductive elements, e.g., printed conductive structures, between thefirst and second thin film-based energy harvesting devices 3204A, 3204Band the first and second electrode layers 112, 120, respectively.

The first and second conductive layers 3220A, 3220B may be transparentwhen the underlying first and second thin film-based energy harvestingdevices 3204A, 3204B include a photovoltaic device. For example, thefirst and second conductive layers 3220A, 3220B may comprise graphene.

In the illustrated embodiment, each of the first and second photovoltaiclayers 3208A, 3208B can have a thickness in a range of about 1-5 μm;each of the first and second electron transport layers 3216A, 3216B canhave a thickness in a range of about 1-2 μm; each of the first andsecond hole transport layers 3212A, 3212B can have a thickness in arange of about 1-10 μm; each of the first and second conductive layers3220A, 3220B can have a thickness in a range of about 10-100 μm; theseparator 116 can have a thickness in a range of about 10-400 μm or10-200 μm; and each of the first and second electrode layers 112, 120can have a thickness of 0.1-2 μm, 0.1-1 μm or 0.5 to 1 μm.

FIG. 34 illustrates a side view of an integrated thin film-basedelectronic device 3400 having integrated therein a thin film-basedenergy storage device (ESD) having laterally adjacent current collectorsand electrode layers, and a thin film-based energy harvesting deviceconfigured to charge/recharge the thin film-based ESD. The thinfilm-based electronic device 3400 is similar to the thin film-basedelectronic device 3200A/3200B described above with respect to FIGS. 32,33, except, the thin film-based electronic device 3400 includes somealternative arrangements of various features. For example, in theillustrated embodiment, a hole transport layer is omitted from each ofthe first and second energy harvesting devices. Thus, the first andsecond energy harvesting devices include first and second photovoltaiclayers 3208A, 3208B, respectively, and first and second electrontransport layers 3216A, 3216B, respectively, but do not include holetransport layers.

In addition, in the illustrated embodiment, the thicknesses of the firstand second electrode layers 112 and 120 are different to accommodate forstoichiometric ratios of the respective electrode active materials, in asimilar manner as described above.

In addition, in some embodiments, one or both of the first and secondphotovoltaic layers 3208A, 3208B comprise an absorbing or activematerial that are formed in a nanoporous insulating material such asdiatom frustules, zeolites, cellulose fibers, fiberglass, or porousalumina, to name a few examples.

Unactivated Thin Film-Based Energy Storage Devices having Extended ShelfLife

A shelf life of an energy storage device is a term used to describe aperiod of time, measured from the time at which the energy storagedevice is manufactured, during which a stored energy storage deviceremains effective, useful, or suitable for consumption. The shelf lifeis measured or calculated from the time the energy storage device ismanufactured, and one of the processes that can shorten the shelf lifeis the self-discharge. The self-discharge can originate, among otherthings, from chemical reactions that occur under open circuit conditionswhen the ESD is not being used. The chemical reactions that contributeto the self-discharge not only include the electrochemical reaction ofthe thin film-based ESD involving the flow of ions that occur under opencircuit conditions, but they also include “side reactions” that are notpart of the electrochemical reaction. External factors such astemperature and humidity during storage can also in turn affect theself-discharge. For example, higher temperatures can accelerate the sidereactions. When the thin film-based ESD is not hermetically sealed orimproperly sealed, the moisture and oxygen from the environment canpromote side reactions in the thin film-based ESD. The inventors haverecognized that, by configuring the thin film-based ESDs such that thechemical effects that give rise to the self-discharge prior to use canbe suppressed and/or delayed, the shelf life of the energy storagedevices can be significantly improved. One way to increase the shelflife is to configure the thin film-based energy storage device such thatan activation process, which may initiate the electrochemical chemicalreactions or the flow of ions that initiate the self-discharge, isdelayed until a user is ready to use the thin film-based ESD. Theactivation may be delayed, e.g., by providing a thin film-based ESDhaving a dry separator without having an electrolyte, and the thinfilm-based ESD can be activated at a later time, e.g., prior to use, byadding the electrolyte. The inventors have recognized that, by usingvarious configurations of thin film-based energy storage devices and themethods of delayed activation described herein, the shelf life can beincreased by at least a year or more.

FIG. 35 illustrates a manufacturing kit 3500 of a thin film-based energystorage device adapted to increase the shelf life. The manufacturing kit3500 includes a thin film-based energy storage device having laterallyadjacent current collectors and electrode layers and a dry separator,and a separately provided electrolyte configured to wet the dryseparator prior to use. The manufacturing kit 3500 includes anunactivated thin film-based energy storage device (ESD) 3520 and anelectrolyte 3508 in a vessel/applicator 3504.

The unactivated thin film-based energy storage device 3520 comprises asubstrate 104 having formed thereon a first current collector 108 and asecond current collector 124 that are disposed laterally adjacent toeach other. The unactivated thin film-based ESD 3520 additionallyincludes a first electrode layer 112 and a second electrode layer 120formed on a first current collector 108 and a second current collector124, respectively. The unactivated thin film-based ESD 3520 additionallyincludes a dry or electrolyteless separator 3516 formed over the firstand second electrode layers 112, 120. Except for the dry separator 3516,other features of the unactivated thin film-based ESD 3520 may besimilar to those described above with respect to FIGS. 2A/2B, and adetailed description of corresponding or similar features is omittedherein for brevity.

Still referring to FIG. 35, the dry separator 3516 is configured toreceive and absorb the electrolyte 3508 throughout the separator 3516 toactivate the thin film-based energy storage device 3520. In someembodiments, the dry separator 3516 comprises or is formed of a porousmaterial that is particularly suited for effectively and rapidlyabsorbing and spreading the electrolyte throughout the dry separator3516. Examples of the porous material that can be used include one ormore of porous and absorbent materials described above, including diatomfrustules, zeolites, cellulose fibers, fiberglass, alumina, silica gel,molecular sieve carbon, natural-clay based solids, polymeric absorbentsor a combination thereof, among other porous and/or absorbent materials.The one or more porous and absorbent materials may be held togetherand/or adhere to the first and second electrode layers 112, 120 usingone or more polymer binders described above. Thus formed dry orelectrolyteless separator 3516 is adapted to rapidly and evenly spreadthe electrolyte 3508 when applied thereto. Special additives, such asone or more surfactants described above, can also be added to the dryseparator 3516 to improve the wetting characteristics of the dryseparator 3516 by the electrolyte 3508.

In some embodiments, the dry separator 3516 may be omitted. For example,in some embodiments, the electrolyte 3508 may simply be spread directlyover the surfaces of the first and second electrode layers 112, 120,thereby creating sufficient ionic bridge for the ion transport betweenthe first and second electrode layers 112, 120.

While in the illustrated embodiment in FIG. 35, the dry separator 3516is formed vertically over the first and second electrode layers 112, 120and laterally therebetween in the gap 210, embodiments are not solimited. In some embodiments, the dry separator 116 may be formed ordeposited, e.g., using a thin film deposition technique, in the gap 210while being omitted from the top surfaces of the first and secondelectrode layers 112, 120. Such arrangement may be especially suitablefor roll-to-roll fabrication techniques.

Still referring to FIG. 35, the electrolyte 3508 is configured to beapplied to the dry separator 3516 to activate the unactivated thinfilm-based ESD 3520. The electrolyte 3508 comprises any suitable liquidelectrolyte described above that is adapted to effectively wet the dryseparator 3512. In some embodiments, the electrolyte 3508 is configuredto have low volatility, which can be advantageous and particularlycompatible with relatively long storage times. For example, by includingan ionic liquid in the electrolyte 3508, the volatility of theelectrolyte 3508 can be significantly reduced, which can in turnsignificantly increase the shelf life. In some embodiments, one or moreadditives described above may be included in the electrolyte 3508 toimprove the spreading or absorbing characteristics of the electrolyte3508. For example, one or more low viscosity additives described abovemay be added to improve the spreading speed of the electrolyte 3508. Insome cases, a surfactant may be added to enhance the rapid spreading. Itwill be appreciated that the disclosed additives can be substantiallyelectrochemically stable.

It will be appreciated that the structural arrangements of various thinfilm-based ESDs having laterally adjacent first and second electrodesdisclosed herein are particularly suitable for implementing themanufacturing kit 3500. For example, the electrolyte 3508 can be appliedand spread more easily when the electrodes are disposed adjacent to eachother, and/or when substantially all of the major surfaces of theelectrodes are exposed to easily receive the electrolyte 3508. Examplesof such arrangements those described above with respect to FIGS. 2A/2B,3A/3B, 9, 10A-10E, 11A, 11B, 12A-12D, 13, 16, 17, 20, 21 and 22.However, embodiments are no so limited, and the concept of activating anunactivated thin film-based ESD can be implemented in other electrodearrangements in which substantially all of the major surfaces of theelectrodes may not be directly exposed, so long as the dry separatorwhen present has an exposed portion through which the electrolyte 3508can be applied. For example, the electrode arrangements described abovewith respect to FIGS. 1, 4, 5, 5, 6, 7, 8, 14A-14D, 15, 18, 19, 23 and24 can be fabricated to have the dry separator that is at leastpartially exposed to receive and absorb the electrolyte, and can thus beimplemented in the manufacturing kit described herein. Furthermore, theintegrated thin film-based electronic devices described above withrespect to FIGS. 25-31 can be fabricated to have the dry separator thatis at least partially exposed to receive and absorb the electrolyte,such that the integrated thin film-based electronic device can beactivated on demand. Similarly, the integrated thin film-basedelectronic devices described above with respect to FIGS. 25-34 can befabricated to have the dry separator of the thin film-based ESD that isat least partially exposed to receive and absorb the electrolyte, suchthat the integrated thin film-based electronic device as a whole can beactivated on demand.

Thus, in various embodiments, because the addition of the electrolyte3508 to the dry separator 3516 is delayed until use, a negligible amountof self-discharge occurs prior to activation of the unactivated thinfilm-based ESD 3520.

It will be appreciated that the delayed activation can be implementedwith any suitable energy storage device chemistry and materials, e.g.,Zn/MnO2-based energy storage devices as disclosed in U.S. Pat. No.9,520,598B2, and Zn/AgO-based energy storage devices as disclosed inU.S. Pat. No. 9,786,926B2, the contents of which are incorporated byreference herein in their entireties.

Still referring to FIG. 35, the electrolyte 3508 may be stored in astorage vessel or applicator 3508 that is particularly suited for easeof storage and application to the unactivated thin film-based ESD 3520.The vessel 3508 may be configured to store a suitable amount of theelectrolyte 3508 that is consistent with the molar mass of theelectrodes 112, 120. Example implementations of the storage vessel 3508,the electrolyte 3504 and the method of activating the unactivated thinfilm-based ESD 3520 using the same include, without limitation:

(1) The vessel 3504 comprising a plastic pouch with a long and thintube. The electrolyte 3508 may be held and prevented from being releasedby a capillary force until a sufficient pressure is applied to the mainbody of the vessel 3508.

(2) The vessel 3504 comprising a sealed plastic vessel having a smallarea that may be weakened. The electrolyte 3508 may be released uponapplication of a pressure to the main body of the plastic vessel,thereby breaking open the weakened area of the plastic vessel. Theweakened portion may arranged to direct the flow of the electrolyte 3508to a desired area of unactivated thin film-based ESD 3520.

(3) The vessel 3504 comprising a plastic vessel that is configured to belocally broken with a sharp sliding wire by puncturing the plasticvessel. The electrolyte 3508 may be released through the puncturedregion of the plastic vessel upon application of a pressure to theplastic vessel.

(4) The vessel 3504 comprising a hard plastic/glass tubing connectedthereto. The tubing can be initially sealed but can be mechanicallybroken by pressure, thereby releasing the electrolyte 3508 through thetubing.

(5) The vessel 3504 comprising a plastic vessel containing a mixture ofthe electrolyte 3508 and microparticles (e.g., microspheres). Theelectrolyte 3508 can be mechanically spread by moving, e.g., rolling,the microparticles.

(6) The vessel 3504 comprising a plastic bag, which holds theelectrolyte 3508 in the form of a foam. The foam can prevent anaccidental spill of the electrolyte 3508. The plastic bag and the foamare configured such that pressing the plastic bag containing the foamreleases the foam.

(7) The vessel 3504 comprising a bag with two clipped sides in themiddle. Upon being bent, the electrolyte 3504 can be released.

(8) The vessel 3504 comprising bag having air in one side thereof. Amechanical pressure applied on the vessel 3504 forces the electrolyte3508 out due to air pressure. In some implementations, the bag has twocompartments, where a first compartment is filled with air, while thesecond compartment is filled with the electrolyte 3508 electrolyte. Amechanical pressure applied to the air in the first compartment in turnresults in a mechanical pressure being applied to the electrolyte 3508of the second compartment, which is forced out of the secondcompartment.

(9) The vessel 3504 comprising a blow tube connected thereto. One end ofthe blow tube can be cut. Blowing into the blow tube can spread theelectrolyte 3508 that is released from the vessel 3504 through aseparate opening.

(10) The vessel 3504 comprising a pull-out bar. The pull-out bar isabsorbent and contains the electrolyte 3508, which may be in the form ofa liquid or foam. Removing (e.g., pulling) the bar moves electrolyteover the top surface of the thin film-based ESD, e.g., the top surfaceof the dry separator 3516 spreads the electrolyte. The pull-out bars canbe magnetic and can be moved with the aid of a magnet.

(11) The vessel 3504 comprising a sponge. The sponge impregnated withthe electrolyte 3508 can be disposed over the dry separator 3516. A thinfilm may be disposed between the sponge and the separator 3516. Uponremoval of the thin film, the electrolyte 3508 can migrate from thesponge to the dry separator 3516.

(12) The vessel 3504 comprising a sponge. The sponge impregnated withthe electrolyte 3508 can be disposed over the dry separator 3516. Adense mesh may be disposed between the sponge and the separator 3516.Upon pressing the sponge, the electrolyte 3508 is delivered to the dryseparator 3516 through the mesh. The electrolyte 3508 may be in the formof a gel in some implementations.

(13) The vessel 3504 comprising a pouch with an opening. The electrolyte3508 is in the form of a gel and disposed inside the vessel 3504. Thegelled electrolyte 3508 can be converted to liquid, e.g., by applicationof heat or mechanically, that can be spread over the dry separator 3516.

(14) The vessel 3504 can comprise gel or polymer capsules in which theelectrolyte 3508 can be encapsulated. The capsules can be initiallyformed over the dry separator 3516, e.g., in a layer. Prior to use, thecapsules can be broken, e.g., by application or heat and/or pressure,thereby releasing the electrolyte 3508 encapsulated in the capsules.While the capsules can have any suitable size, it will be appreciatedthat when the capsules smaller than 50 microns, they can be particularlyadapted for being formed on the dry separator 3516 by printing.

It will be appreciated that the above implementations of the vessel3504, the electrolyte 3508 and the methods of activating the unactivatedthin film-based ESD 3520 using the same are provided as examples, andany other suitable implementations may be used. Furthermore, it will beappreciated that one or more vessels 3504 and a combination of differentvessels 3504 can be used in some implementations, e.g., in circumstanceswhere the surface area on which the electrolyte 3508 is to be applied isrelatively large.

In some implementations, the vessel 3504 may be positioned in the middleof the unactivated thin film-based energy storage device 3520. Severalperforations/holes/tubes may be formed in the vessel 3504 to facilitatethe spread of the electrolyte 3508 evenly over the surface of the dryseparator 3516.

Still referring to FIG. 35, in some embodiments, the manufacturing kit3500 of a thin film-based energy storage device is configured to produceone-time use thin film devices. However, embodiments are not so limitedand the manufacturing kit 3500 can be configured to produce multiple-usethin film electronic devices.

The manufacturing kit 3500 can provide several possible advantages tothe thin film-based energy storage device 3520 as well as any thinfilm-based electronic device connected thereto or integrated therewith,including without limitation:

(1) An intrinsic activation mechanism. Upon application of theelectrolyte 3508, the unactivated thin film-based ESD is “switch on.”

(2) A long shelf life. Degradation mechanisms such as self-discharge isreduced by delaying activation.

(3) Integration with a core device. The core device powered by the thinfilm-based ESD can be formed and integrated on the same substrate.

(4) Internal resistance control. The internal resistance of the thinfilm-based ESD can be controlled by the design of the thin film-basedESD itself, without additional external resistors, e.g., resistorsconnected in parallel.

(5) High manufacturability. The thin film-based ESD is easy to fabricateby, e.g., printing using roll-to-roll thin film manufacturingtechniques. The electrode coverage areas can be adjusted for differentstoichiometries of different electrochemical reactions, instead ofhaving to vary the relative thicknesses of the electrodes in “oneelectrode on top of the other” designs.

(6) Easy packaging. Thin film-based ESDs having adjacently disposedelectrodes are relatively easier to package and integrate with otherprinted devices.

(7) Ease of stoichiometric adjustment of electrode active materials. Asdescribed above the stochiometric proportions between electrodes can berelatively easily adjusted. Not every some embodiments may include some,all, or none of the listed advantages, and other advantages are alsopossible.

Additional Embodiments

1. A method of fabricating an energy storage device, the methodcomprising:

-   -   printing laterally adjacent and electrically separated current        collector layers including a first current collector layer and a        second current collector layer over a substrate;    -   printing an electrode layer of a first type over the first        current collector layer;    -   printing an electrode layer of a second type over the second        current collector layer; and    -   printing a separator over one or both of the electrode layers of        the first and second types, wherein printing the separator        includes printing over exposed surfaces of one or both of the        electrode layers of the first and second types,    -   wherein the electrode layer of the first type comprises a first        electrode active material and the electrode layer of the second        type comprises a second electrode active material, and wherein a        molar ratio between the first electrode active material and the        second electrode active material is between 0.25 and 4.0.

2. The method of Embodiment 1, wherein printing the current collectorlayers comprises simultaneously printing the first current collectorlayer and the second current collector layer.

3. The method of Embodiments 1 or 2, wherein printing the separatorcomprises simultaneously printing over the exposed surfaces of both ofthe electrode layers of the first and second types.

4. The method of any one of Embodiments 1-3, comprising adjusting aprinted area of the electrode layer of the first type and a printed areaof the electrode layer of the second type according to the molar ratio.

5. The method of any one of Embodiments 1-4, wherein printing theseparator comprises printing over the exposed surfaces of the electrodelayer of the first type prior to printing the electrode layer of thesecond type, and wherein printing the electrode layer of the second typecomprises printing over the separator and over the second currentcollector layer.

6. The method of any one of Embodiments 1-5, wherein four printing stepscomprise printing the first and second current collector layers,printing the electrode layers of the first and second types and printingthe separator.

7. The method of any one of Embodiments 1-6, wherein the substrate orthe separator comprises perforations.

8. The method of Embodiment 7, wherein the separator comprises theperforations, wherein the method comprises printing the separatorsimultaneously over the electrode layers of the first and second types,and wherein the method further comprises one or both of:

-   -   printing a further first electrode layer over the separator and        over the first electrode, wherein the further first electrode        layer fills the perforations in contact therewith, the first        electrode layer and the further first electrode layer on        opposite sides of the separator and electrically connected to        each other; and    -   printing a further second electrode layer over the separator and        over the second electrode, wherein the further second electrode        layer fills the perforations in contact therewith, the second        electrode layer and the further second electrode layer on        opposite sides of the separator and electrically connected to        each other.

9. The method of Embodiment 7, wherein the substrate comprises theperforations, the method further comprising:

-   -   simultaneously printing a further first current collector layer        and a further second current collector layer over an opposite        side of the substrate,        -   wherein the further first current collector layer fills the            perforations in contact therewith, the first current            collector layer and the further first current collector            layer on opposite sides of the substrate and electrically            connected to each other, and        -   wherein the further second current collector layer fills the            perforations in contact therewith, the second electrode            layer and the further second electrode layer on opposite            sides of the separator and electrically connected to each            other;    -   printing a second electrode layer of the first type over the        further first current collector layer at the opposite side of        the substrate;    -   printing a second electrode layer of the second type over the        further second current collector layer at the opposite side of        the substrate; and    -   printing a further separator over one or both of the second        electrode layer of the first type and the second electrode layer        of the second type.

10. The method of any one of Embodiments 1-9, wherein the first currentcollector layer comprises a plurality of first finger structures and thesecond current collector layer comprises a plurality of second fingerstructures, wherein the first finger structures and the second fingerstructures are interlaced to alternate in a lateral direction.

11. The method of Embodiment 10, wherein printing the separatorcomprises simultaneously printing over the exposed surfaces of both ofthe electrode layers of the first and second types.

12. The method of Embodiment 10, wherein printing the separatorcomprises printing over the exposed surfaces of the electrode layer ofthe first type prior to printing the electrode layer of the second type,and wherein printing the electrode layer of the second type comprisesprinting over the separator and over the second current collector layer.

13. The method of any one of Embodiments 1-12, further comprisingconfiguring the first current collector layer as a first currentcollector having a first polarity and the second current collector layerserves as a second current collector having a second polarity.

14. The method of any one of Embodiments 1-13, further comprising:

-   -   printing a third current collector layer laterally between the        first and second current collector layers;    -   printing a second electrode layer of the first type over the        third current collector layer;    -   printing a second electrode layer of the second type over the        third current collector layer; and    -   printing a second separator over one or both of the second        electrode layers of the first and second types, wherein printing        the separator includes printing over exposed surfaces of one or        both of the second electrode layers of the first and second        types.

15. The method of Embodiment 14, wherein printing the third currentcollector layer comprises simultaneously printing with the first andsecond current collector layers.

16. The method of Embodiment 14, wherein printing the second electrodelayer of the first type comprises simultaneously printing with theelectrode layer of the first type.

17. The method of Embodiment 14, wherein printing the second electrodelayer of the second type comprises simultaneously printing with theelectrode layer of the second type.

18. The method of Embodiment 14, wherein printing the separatorcomprises simultaneously printing with the second separator.

19. The method of Embodiment 18, wherein printing the separator and thesecond separator comprises simultaneously printing over the exposedsurfaces of both of the electrode layers of the first and second typesand both of the second electrode layers of the first and second types.

20. The method of Embodiment 18, wherein printing the separator and thesecond separator comprise simultaneously covering exposed surfaces ofthe electrode layer of the first type and the second electrode layer ofthe first type prior to printing the electrode layer of the second typeand the second electrode layer of the second type, and wherein printingthe electrode layer of the second type and the second electrode layer ofthe second type comprises simultaneously printing over the separator,the second separator, the second current collector layer, and the thirdcurrent collector layer.

21. A method of fabricating an energy storage device, the methodcomprising:

-   -   printing a plurality of laterally adjacent and electrically        separated current collector layers over a substrate;    -   printing electrode layers of a first type over at least a first        subset of the plurality of current collector layers;    -   printing electrode layers of a second type over at least a        second subset of the plurality of current collector layers; and    -   printing a plurality of separator layers to form a plurality of        electrically connected cells of the energy storage device,        wherein each of the cells comprises one separator of the        plurality of separator layers contacting one of the electrode        layers of the first type and one of the electrode layers of the        second type.

22. The method of Embodiment 21, wherein printing the current collectorlayers comprises simultaneously printing the current collector layers.

23. The method of Embodiments 21 or 22, wherein printing the electrodelayers of the first type comprises simultaneously printing the electrodelayers of the first type.

24. The method of any one of Embodiments 21-23, wherein printing theelectrode layers of the second type comprises simultaneously printingthe electrode layers of the second type.

25. The method of any one of Embodiments 21-24, wherein printing theseparator layers comprises simultaneously printing the separator layers.

26. The method of any one of Embodiments 21-25, wherein printing theplurality of separator layers comprises simultaneously covering exposedsurfaces of the electrode layers of the first type and the electrodelayers of the second type.

27. The method of any one of Embodiments 21-26, wherein printing theplurality of separator layers comprises simultaneously covering exposedsurfaces of the electrode layers of the first type prior to printing theelectrode layers of the second type, and wherein printing the electrodelayers of the second type comprises printing over the plurality ofseparators and over corresponding ones of the second subset of theplurality of current collector layers.

28. The method of any one of Embodiments 21-27, wherein printing theplurality of current collector layers comprises printing two outercurrent collector layers configured to serve as positive and negativecurrent collectors and printing one or more inner current collectorlayers laterally between the outer collector layers, wherein each of theone or more inner current collector layers is shared between twoadjacent cells of the plurality of cells.

29. The method of any one of Embodiments 21-28, wherein each of the oneor more inner current collector layers has thereover one of theelectrode layer of the first type and one of the electrode layers of thesecond type, such that adjacent ones of the plurality of cells areelectrically connected in series.

30. The method of any one of Embodiments 21-29, wherein printing theplurality of current collector layers comprises printing linearly alonga line.

31. The method of any one of Embodiments 21-30, wherein printing theplurality of current collector layers comprises printing concentriccircular layers.

32. The method of any one of Embodiments 21-31, wherein the plurality ofelectrically connected cells are configured to be detached from eachother upon receiving a mechanical force.

33. The method of Embodiment 32, wherein the plurality of electricallyconnected cells are configured to be detached at boundaries betweenadjacent cells of the plurality of cells, wherein the boundariescomprise weakened structures adapted for separation upon receiving themechanical force.

34. The method of any one of Embodiments 21-33, wherein the energystorage device is flexible.

35. The method of any one of Embodiments 21-34, wherein the plurality ofelectrically connected cells are configured as a wearable bracelet.

36. The method of Embodiment 35, comprising connecting the plurality ofelectrically connected cells to a load device configured to be poweredby the plurality of electrically connected cells.

37. A manufacturing kit for an energy storage device, comprising:

-   -   an unactivated energy storage device comprising:        -   a substrate,        -   a plurality of laterally adjacent and electrically separated            current collector layers over the substrate, the plurality            of current collector layers including a first current            collector layer and a second current collector layer,        -   an electrode layer of a first type over the first current            collector layer,        -   an electrode layer of a second type over the second current            collector layer, and        -   a dry separator over one or both of the electrode layers of            the first and second types, wherein the separator comprises            an exposed portion through which the dry separator is            configured to receive an electrolyte; and    -   an electrolyte configured to be applied to the unactivated        energy storage device to activate the energy storage device.

38. The manufacturing kit of Embodiment 37, wherein the dry separatorcomprises pores configured to absorb the electrolyte upon being applied.

39. The manufacturing kit of Embodiments 37 or 38, wherein theelectrolyte comprises an ionic liquid.

40. The manufacturing kit of any one of Embodiments 37-39, wherein thedry separator is over both of the electrode layers of the first andsecond types.

41. The manufacturing kit of any one of Embodiments 37-40, wherein thedry separator is over the electrode layer and the electrode layer of thesecond type is over the separator and extends over the second currentcollector layer.

42. A method of fabricating an electrical system, the method comprising:

-   -   printing an energy storage device over a battery-powered core        device over a substrate, the battery-powered core device        configured to receive power through a first power terminal and a        second terminal, the energy storage device configured to provide        the power to the battery-powered core device, wherein printing        the energy storage device comprises:        -   printing a plurality of current collector layers including a            first current collector layer and a second current collector            layer, wherein at least one of the first or second current            collector layers is printed over the first and second power            terminals,        -   printing an electrode layer of a first type over the first            current collector layer,        -   printing an electrode layer of a second type over the second            current collector layer, and        -   printing a separator over exposed surfaces of one or both of            the electrode layers of the first and second types.

43. The method of Embodiment 42, wherein printing the plurality ofcurrent collector layers includes printing the first current collectorlayer over the first power terminal and printing the second currentcollector layer over the second power terminal.

44. The method of Embodiments 42 or 43, wherein printing the separatorcomprises printing over the exposed surfaces of both of the electrodelayers of the first and second types.

45. The method of any one of Embodiments 42-44, wherein printing theseparator comprises printing over the exposed surfaces of the electrodelayer of the first type prior to printing the electrode layer of thesecond type, and wherein printing the electrode layer of the second typecomprises printing over the separator and over the second currentcollector layer.

46. The method of any one of Embodiments 42-45, further comprisingforming the core device over the substrate.

47. An energy storage device comprising:

-   -   a first current collector layer and a second current collector        layer adjacently disposed in a lateral direction over an        electrically insulating substrate;    -   a first electrode layer of a first type over the first current        collector layer;    -   a separator over the first electrode layer; and    -   a second electrode layer of a second type different from the        first type comprising over the separator,    -   wherein the second electrode layer comprises a base portion        extending from the second current collector layer in a vertical        direction and a lateral extension portion laterally extending        from the base portion in the lateral direction to overlap the        first electrode layer,    -   wherein one or more of the first current collector layer, the        first electrode layer, the separator, the second electrode layer        and the second current collector layer is a printed layer.

48. The energy storage device of Embodiment 47, wherein the electricallyinsulating substrate comprises a polymeric substrate.

49. The energy storage device of Embodiments 47 or 48, wherein theelectrically insulating substrate comprises a flexible substrate.

50. The energy storage device of any one of Embodiments 47-49, whereinthe separator comprises:

-   -   a vertical portion interposed in the lateral direction between        the base portion of the second electrode layer and a side        surface of the first electrode layer; and    -   a horizontal portion interposed in the vertical direction        between the lateral extension portion of the second electrode        layer and a top surface of the first electrode layer.

51. The energy storage device of any one of Embodiments 47-50, whereinthe base portion of the second electrode layer has a width that isthicker than a thickness of the lateral extension portion of the secondelectrode layer.

52. The energy storage device of Embodiment 51, wherein the width of thebase portion of the second electrode layer is greater than the thicknessof the lateral extension portion of the second electrode layer by afactor between two to ten.

53. The energy storage device of any one of Embodiments 47-52, whereinthe first electrode layer comprises a first electrode active materialand the second electrode layer comprises a second electrode activematerial, wherein a molar ratio between the first electrode activematerial and the second electrode active material is between 0.25 and4.0.

54. The energy storage device of any one of Embodiments 47-53, whereinprinted ones of the one or more of the first current collector layer,the first electrode layer, the separator, the second electrode layer andthe second current collector layer comprise a dried ink composition.

55. An energy storage device comprising:

-   -   a first current collector layer and a second current collector        layer adjacently disposed in a lateral direction over an        electrically insulating substrate;    -   a first electrode layer of a first type over the first current        collector layer;    -   a second electrode layer of a second type over the second        current collector layer; and    -   a separator over the first electrode layer and the second        electrode layer,    -   wherein one or more of the first current collector layer, the        first electrode layer, the separator, the second electrode layer        and the second current collector layer are printed layers,    -   wherein the first electrode layer comprises a first electrode        active material and the second electrode layer comprises a        second electrode active material, and wherein a molar ratio        between the first electrode active material and the second        electrode active material is between 0.25 and 4.0.

56. The energy storage device of Embodiment 55, wherein the firstelectrode layer comprises a first electrode active material and thesecond electrode layer comprises a second electrode active material,wherein a ratio between a lateral coverage area of the first electrodelayer and a lateral coverage area of the second electrode isproportional to the molar ratio.

57. The energy storage device of Embodiments 55 or 56, wherein the firstelectrode layer is on a first side of the separator, and wherein theenergy storage device further comprises a further first electrode layeron a second side of the separator opposite the first side of theseparator.

58. The energy storage device of Embodiment 57, wherein the firstelectrode layer and the further first electrode layer are electricallyconnected to each other.

59. The energy storage device of Embodiment 58, wherein the firstelectrode layer and the further first electrode layer are electricallyconnected to each other through a plurality of perforations through aportion of the separator between the first electrode layer and thefurther first electrode layer.

60. The energy storage device of Embodiment 59, wherein one or both ofthe first electrode layer and the further first electrode layer fillsthe plurality of perforations.

61. The energy storage device of any one of Embodiments 55-60, whereinthe second electrode layer is on a first side of the separator, andwherein the energy storage device further comprises a further secondelectrode layer on a second side of the separator opposite the firstside of the separator.

62. The energy storage device of Embodiment 61, wherein the secondelectrode layer and the further second electrode layer are electricallyconnected to each other.

63. The energy storage device of Embodiment 62, wherein the secondelectrode layer and the further second electrode layer are electricallyconnected to each other through a plurality of perforations through aportion of the separator between the second electrode layer and thefurther second electrode layer.

64. The energy storage device of Embodiment 63, wherein one or both ofthe second electrode layer and the further second electrode layer fillsthe plurality of perforations.

65. The energy storage device of any one of Embodiments 55-64, whereinthe first current collector layer is on a first side of the electricallyinsulating substrate, and wherein the energy storage device furthercomprises a further first current collector layer on a second side ofthe electrically insulating substrate opposite the first side of theelectrically insulating substrate.

66. The energy storage device of Embodiment 65, wherein the firstcurrent collector layer and the further first current collector layerare electrically connected to each other.

67. The energy storage device of Embodiment 66, wherein the firstcurrent collector layer and the further first current collector layerare electrically connected to each other through a plurality ofperforations through a portion of the electrically insulating substratebetween the first current collector layer and the further first currentcollector layer.

68. The energy storage device of Embodiment 67, wherein one or both ofthe first current collector layer and the further first currentcollector layer fills the perforations.

69. The energy storage device of any one of Embodiments 55-68, whereinthe second current collector layer is on a first side of theelectrically insulating substrate, and wherein the energy storage devicefurther comprises a further second current collector layer on a secondside of the electrically insulating substrate opposite the first side ofthe electrically insulating substrate.

70. The energy storage device of Embodiment 69, wherein the secondcurrent collector layer and the further second current collector layerare electrically connected to each other.

71. The energy storage device of Embodiment 70, wherein the secondcurrent collector layer and the further second current collector layerare electrically connected to each other through a plurality ofperforations through a portion of the electrically insulating substratebetween the second current collector layer and the further secondcurrent collector layer.

72. The energy storage device of Embodiment 71, wherein one or both ofthe first current collector layer and the further first currentcollector layer fills the perforations.

73. The energy storage device of any one of Embodiments 55-72, whereinthe first current collector layer and the second current collector areon a first side of the electrically insulating substrate, and whereinthe energy storage device further comprises a further first currentcollector layer and a further second current collector layer on a secondside of the electrically insulating substrate opposite the first side ofthe electrically insulating substrate.

74. The energy storage device of Embodiment 73, further comprising:

-   -   a further first electrode layer of the first type over the        further first current collector layer;    -   a further second electrode layer of the second type over the        further second current collector layer; and    -   a further separator over the further first electrode layer and        the further second electrode layer.

75. The energy storage device of Embodiment 74, wherein the separatorand the further separator are physically connected through a pluralityof perforations through the electrically insulating substrate.

76. An energy storage device comprising:

-   -   a first current collector layer over an electrically insulating        substrate;    -   a first electrode layer of a first type over the first current        collector layer;    -   a separator over the first electrode layer and covering a top        surface and a side surface thereof;    -   a second electrode layer of a second type over the separator;        and    -   a second current collector layer comprising a base portion        extending from the electrically insulating substrate in a        vertical direction and a lateral extension portion laterally        extending from the base portion in the lateral direction to        overlap the second electrode layer,    -   wherein one or more of the first current collector layer, the        first electrode layer, the separator, the second electrode layer        and the second current collector layer are printed layers,    -   wherein the first electrode layer comprises a first electrode        active material and the second electrode layer comprises a        second electrode active material, and wherein a molar ratio        between the first electrode active material and the second        electrode active material is between 0.25 and 4.0.

77. The energy storage device of Embodiment 76, wherein the secondelectrode layer is on a first side of the second current collector, andwherein the energy storage device further comprises a further secondelectrode layer on a second side of the second current collectoropposite the first side of the second current collector.

78. The energy storage device of Embodiment 77, wherein the secondelectrode layer and the further second electrode layer are electricallyconnected to each other.

79. The energy storage device of Embodiment 78, wherein the secondelectrode layer and the further second electrode layer are electricallyconnected to each other through a plurality of perforations through thelateral extension portion of the second current collector between thesecond electrode layer and the further second electrode layer.

80. The energy storage device of Embodiment 79 wherein one or both ofthe second electrode layer and the further second electrode layer fillsthe plurality of perforations.

81. The energy storage device of any one of Embodiments 76-80, furthercomprising:

-   -   a second separator over the further second electrode layer;    -   a further first electrode layer over the second separator; and    -   a further first current collector layer over the first electrode        layer.

82. The energy storage device of Embodiment 81, wherein the firstcurrent collector layer and the further first current collector layerare electrically connected to each other.

83. An energy storage device comprising:

-   -   an electrically insulating substrate;    -   a first current collector over the electrically insulating        substrate, wherein the first current collector comprises a        plurality of first current collector finger structures;    -   a second current collector over the electrically insulating        substrate, wherein the second current collector comprises a        plurality of second current collector finger structures, wherein        the first current collector finger structures and the second        current collector finger structures are interleaved to alternate        in a lateral direction;    -   a first electrode layer of a first type over the first current        collector layer;    -   a second electrode layer of a second type over the second        current collector layer; and    -   a separator layer separating the first electrode layer and the        second electrode layer.

84. The energy storage device of Embodiment 83, wherein the firstelectrode layer comprises a first electrode active material and thesecond electrode layer comprises a second electrode active material,wherein a molar ratio between the first electrode active material andthe second electrode active material is between 0.25 and 4.0.

85. The energy storage device of Embodiments 83 or 84, wherein the firstelectrode layer comprises a first electrode active material and thesecond electrode layer comprises a second electrode active material,wherein a ratio between a lateral area of the first electrode layer anda lateral area of the second electrode is proportional to the molarratio.

86. The energy storage device of any one of Embodiments 83-85, whereinthe first electrode layer comprises a plurality of first electrodefinger structures and the second electrode layer comprises a pluralityof second electrode finger structures, and wherein the first electrodefinger structures and the second electrode finger structures areinterleaved to alternate in the lateral direction.

87. The energy storage device of Embodiment 86, wherein the separatorlayer is over the first electrode layer and the second electrode layer.

88. The energy storage device of Embodiment 87, wherein the separatorlayer is interposed between adjacent pairs of the first electrode fingerstructures and the second electrode finger structures that alternate inthe lateral direction.

89. The energy storage device of Embodiment 88, wherein the separatorlayer is interposed between adjacent pairs of the first currentcollector finger structures and the second current collector fingerstructures that alternate in the lateral direction.

90. The energy storage device of any one of Embodiments 83-89, whereinthe first electrode layer comprises a plurality of first electrodefinger structures, wherein the separator layer is over each of the firstelectrode finger structures, and wherein the second electrode layer isover the separator layer.

91. The energy storage device of Embodiment 90, wherein the separatorseparates the first electrode finger structures from the secondelectrode layer in the lateral direction and in the a verticaldirection.

92. The energy storage device of Embodiment 91, wherein the separatorlayer is interposed between adjacent pairs of the first currentcollector finger structures and the second current collector fingerstructures that alternate in the lateral direction.

93. The energy storage device of any one of Embodiments 83-92, whereineach of the first current collector finger structures and the secondcurrent collector finger structures has a ratio of a length to a widthbetween about 2 and 100.

94. An energy storage device comprising:

-   -   a plurality of laterally adjacent and electrically separated        current collectors over an electrically insulating substrate,    -   wherein the energy storage device comprises a plurality of        electrically connected energy storage cells, and    -   wherein each of the energy storage cells comprises a first        electrode layer of a first type on one of the current        collectors, a second electrode layer of a second type on an        adjacent one of the current collectors, and a separator        contacting and electrically separating the first electrode layer        and the second electrode layer.

95. The energy storage device of Embodiment 94, wherein adjacent ones ofthe energy storage cells share a common current collector layer havingthereon the first electrode layer of a first one of the adjacent ones ofthe energy storage cells and the second electrode layer of the secondone of the adjacent ones of the energy storage cells.

96. The energy storage device of Embodiments 94 or 95, wherein theplurality of current collectors comprises a first current collectorconfigured to serve as a current collector of a first polarity, a secondcurrent collector configured to serve as a current collector of a secondpolarity, and one or more intermediate current collectors configured toelectrically connect the adjacent ones of the energy storage cells.

97. The energy storage device of any one of Embodiments 94-96, whereineach of the intermediate current collectors has thereon one of the firstelectrode layers and one of the second electrode layers that are notelectrically separated by one of the separator layers.

98. The energy storage device of any one of Embodiments 94-97, whereineach of the energy storage cells comprises one of the first electrodelayers having a first electrode active material and one of the secondelectrode layers having a second electrode active material, wherein amolar ratio between the first electrode active material and the secondelectrode active material is between 0.25 and 4.0.

99. The energy storage device of Embodiment 98, wherein each of theenergy storage cells has a ratio between a lateral area of the firstelectrode layer and a lateral area of the second electrode that isproportional to the molar ratio.

100. The energy storage device of any one of Embodiments 94-99, whereinin each of the energy storage cells, the separator contacts top surfacesof the first electrode layer and the second electrode layer.

101. The energy storage device of any one of Embodiments 94-100, whereinin each of the energy storage cells, the separator is over the firstelectrode layer and the second electrode layer is over the separator.

102. The energy storage device of Embodiment 101, wherein the secondelectrode layer of a first one of the energy storage cells comprises abase portion extending from the adjacent one of the current collectorsin a vertical direction and a lateral extension portion laterallyextending from the base portion in the lateral direction to overlap thefirst electrode layer on the one of the current collectors.

103. The energy storage device of any one of Embodiments 94-102, whereinthe plurality of current collectors are along a line.

104. The energy storage device of any one of Embodiments 94-103, whereinthe plurality of current collector comprise concentric layers.

105. The energy storage device of any one of Embodiments 94-104, whereinthe energy storage device is flexible and configured to be worn by auser.

106. The energy storage device of any one of Embodiments 94-105, whereinthe plurality of electrically connected energy storage cells isconfigured to be worn by a user as a wearable bracelet.

107. The energy storage device of any one of Embodiments 94-106, whereinthe plurality of electrically connected energy storage cells isconfigured to be electrically connected to a core device powered by theenergy storage device.

108. The energy storage device of Embodiment 107, wherein the coredevice comprises a device selected from the group consisting of a lightemitting device, an active or passive radio frequency identificationdevice, a Bluetooth® device, a sensor, an infrared (IR) device,interface electronics, a Zigbee®-based device, a near-fieldcommunication (NFC)-based device, a health indicator monitor and alocation tracking device.

109. The energy storage device of any one of Embodiments 94-108, whereinthe electrically connected energy storage cells are configured to bedetached from each other upon receiving a mechanical force to form aregular pattern of electrically connected energy storage cells.

110. The energy storage device of Embodiment 109, wherein the pluralityof electrically connected energy storage cells are configured to bedetached at boundaries between adjacent ones of the plurality ofelectrically connected energy storage cells, wherein the boundariescomprise weakened structures in the electrically insulating substratethat are adapted for separation upon receiving the mechanical force.

111. The energy storage device of Embodiment 110, wherein the pluralityof electrically connected energy storage cells are arranged as one ormore rows of electrically connected energy storage cells and one or morecolumns of electrically connected energy storage cells.

112. The energy storage device of Embodiment 111, wherein each of theone or more rows of electrically connected energy storage cells areelectrically connected in series, and wherein each of the one or morecolumns of electrically connected energy storage cells are electricallyconnected in parallel.

113. A method of activating an energy storage device, comprising:

-   -   providing an unactivated energy storage device comprising:        -   a substrate,        -   a plurality of laterally adjacent and electrically separated            current collector layers over the substrate, the plurality            of current collector layers including a first current            collector layer and a second current collector layer,        -   an electrode layer of a first type over the first current            collector layer,        -   an electrode layer of a second type over the second current            collector layer, and        -   a dry separator over one or both of the electrode layers of            the first and second types, wherein the separator comprises            an exposed portion through which the dry separator is            configured to receive an electrolyte; and    -   activating the energy storage device by applying an electrolyte        to the dry separator.

114. The method of Embodiment 113, wherein activating comprisesabsorbing the electrolyte into the dry separator comprising pores.

115. The method of Embodiments 113 or 114, wherein the electrolytecomprises an ionic liquid.

116. The method of any one of Embodiments 113-115, wherein the dryseparator is over both of the electrode layers of the first and secondtypes.

117. The method of any one of Embodiments 113-116, wherein the dryseparator is over the electrode layer and the electrode layer of thesecond type is over the separator and extends over the second currentcollector layer.

118. A thin film-based electronic device, comprising:

-   -   a thin film-based core device and a thin film-based energy        storage device (ESD) electrically connected to each other,        wherein the thin film-based core device and the thin film-based        energy storage device are integrated on a common substrate and        overlap each other in a direction normal to the common        substrate.

119. The thin film-based electronic device of Embodiment 118, whereinthe thin film-based ESD comprises a first current collector layer and asecond current collector layer that are adjacently disposed relative toeach other, a first electrode layer of a first type over the firstcurrent collector layer, a second electrode layer of a second type overthe second current collector layer, and a separator over one or both ofthe first and second electrode layers.

120. The thin film-based electronic device of Embodiment 119, whereinthe thin film-based core device is vertically interposed between thecommon substrate and one or more of the first current collector layer,the second current collector layer, the first electrode layer, thesecond electrode layer or the separator.

121. The thin film-based electronic device of Embodiment 120, whereinseparator is over the first electrode layer and the second electrodelayer.

122. The thin film-based electronic device of Embodiment 121, whereinthe thin film-based core device is vertically interposed between thecommon substrate and both of the first and second current collectorlayers.

123. The thin film-based electronic device of Embodiments 121 or 122,wherein the thin film-based core device is vertically interposed betweenthe common substrate and both of the first and second electrode layers.

124. The thin film-based electronic device of any one of Embodiments121-123, wherein the thin film-based core device is configured toreceive power through a first terminal and a second terminal thereon,and wherein the first electrode layer is over the first terminal and thesecond electrode layer is over the second terminal.

125. The thin film-based electronic device of any one of Embodiments121-123, wherein the thin film-based core device is configured toreceive power through a first terminal and a second terminal on the sameside of the thin film-based core device.

126. The thin film-based electronic device of any one of Embodiments121-125, wherein the thin film-based core device is verticallyinterposed between the common substrate and each of the first currentcollector layer, the second current collector layer, the first electrodelayer, the second electrode layer and the separator.

127. The thin film-based electronic device of Embodiment 121, whereinthe thin film-based core device is vertically interposed between thecommon substrate and one but not the other of the first and secondcurrent collector layers.

128. The thin film-based electronic device of Embodiments 121 or 127,wherein the thin film-based core device is vertically disposed betweenthe common substrate and one but not the other of the first and secondelectrode layers.

129. The thin film-based electronic device of Embodiments 127 or 128,wherein the thin film-based core device is configured to receive powerthrough a first terminal and a second terminal thereon, and wherein thefirst electrode layer is over the first terminal and the secondelectrode layer is over the second terminal.

130. The thin film-based electronic device of Embodiments 127 or 128,wherein the thin film-based core device is configured to receive powerthrough a first terminal and a second terminal on opposing sides thethin film-based core device.

131. The thin film-based electronic device of any one of Embodiments127-130, wherein the thin film-based core device is verticallyinterposed between the common substrate and each of the first currentcollector layer, the first electrode layer and the separator.

132. The thin film-based electronic device of Embodiment 118, whereinthe thin film-based ESD comprises:

-   -   a first current collector layer over the common substrate;    -   a first electrode layer of a first type over the first current        collector layer;    -   a separator over the first electrode layer;    -   a second electrode layer of a second type over the separator;        and    -   a second current collector layer over the second electrode        layer.

133. The thin film-based electronic device of Embodiment 132, whereinthe thin film-based core device is vertically interposed between thefirst current collector layer and the second current collector layer.

134. The thin film-based electronic device of Embodiments 132 or 133,wherein the thin film-based core device is configured to receive powerthrough a first terminal and a second terminal thereon, and wherein thefirst terminal is over the first current collector layer and the secondcurrent collector layer is over the second terminal.

135. The thin film-based electronic device of Embodiments 132 or 133,wherein the thin film-based core device is configured to receive powerthrough a first terminal and a second terminal on opposing sides thethin film-based core device.

136. The thin film-based electronic device of any one of Embodiments118-135, wherein the common substrate comprises an electricallyinsulating substrate.

137. The thin film-based electronic device of any one of Embodiments118-136, wherein the common substrate comprises a flexible substrate.

138. The thin film-based electronic device of any one of Embodiments118-137, wherein the first electrode layer comprises a first electrodeactive material and the second electrode layer comprises a secondelectrode active material, and wherein a molar ratio between the firstelectrode active material and the second electrode active material isbetween 0.25 and 4.0.

139. The thin film-based electronic device of any one of Embodiments118-138, wherein the thin film-based core device comprises one or moreof a light emitting device, an acoustic device, a monitor device, amotor device, a movement device, a display device, an antenna, an activeor passive radio frequency identification (RFID) device, a Bluetooth®device, a sensor, an infrared (IR) device, interface electronics, aZigbee®-based device, an A-wave device, a near-field communication(NFC)-based device, a smart band, a health monitor, a fitness trackingdevice, a smart watch, a position tracking device, a low power wirelesspersonal area network (LoWPAN) device or a low power wide area network(LPWAN) device.

140. The thin film-based electronic device of any one of Embodiments118-139, wherein the thin film-based core device comprises a lightemitting device.

141. The thin film-based electronic device of Embodiment 140, whereinthe common substrate is a transparent substrate configured to transmittherethrough light emitted by the light emitting device.

142. The thin film-based electronic device of any one of Embodiments118-141, further comprising an activation switch configured to activatea circuit comprising the thin film-based core device and the thinfilm-based ESD.

143. A thin film-based electronic device, comprising:

-   -   a thin film-based energy storage device (ESD); and    -   a thin film-based energy harvesting device and electrically        connected to the thin film-based ESD and configured to charge        the thin film-based ESD,    -   wherein the thin film-based energy harvesting device and the        thin film-based energy storage device are integrated on a common        substrate.

144. The thin film-based electronic device of Embodiment 143, whereinthe thin film-based ESD comprises a first current collector layer and asecond current collector layer that are disposed laterally adjacent toeach other, a first electrode layer of a first type vertically over thefirst current collector layer, a second electrode layer of a second typevertically over the second current collector layer, and a separatorseparating the first and second current collector layers and separatingthe first and second electrode layers.

145. The thin film-based electronic device of Embodiment 144, whereinthe separator is laterally interposed between the first and secondelectrode layers.

146. The thin film-based electronic device of Embodiments 144 or 145,wherein the separator is laterally interposed between the first andsecond current collector layers.

147. The thin film-based electronic device of Embodiment 146, whereinthe thin film-based energy harvesting device is disposed vertically overone or both of the first electrode and the second electrode layers.

148. The thin film-based electronic device of any one of Embodiments 143to 147, wherein the thin film-based energy harvesting device comprisesone or more of a photovoltaic device, a thermoelectric device, apiezoelectric device, a wireless charging device, a tribologicalharvesting device, an RF-based energy harvesting device, a pyroelectricenergy harvesting device, a capacitive energy harvesting device, amicrobial energy harvesting device or magnetorestrictive energyharvesting device.

149. The thin film-based electronic device of any one of Embodiments 143to 148, wherein the thin film-based energy harvesting device comprises aprinted photovoltaic layer.

150. The thin film-based electronic device of Embodiment 149, whereinthe printed photovoltaic layer comprises an organic-inorganic hybridmaterial having a perovskite crystal structure.

151. The thin film-based electronic device of Embodiment 149, whereinthe printed photovoltaic layer comprises an organic-inorganic hybridmaterial having a chemical formula ABX₃, where A is an organic orinorganic cation, B is a metal cation and X is an anion.

152. The thin film-based electronic device of Embodiment 151, wherein Ais one of methylammonium, formamidinium or Cs⁺, B is one of Pb2⁺ orSn²⁺, and X is one of I⁻, Br—, Cl⁻ or SCN⁻.

153. The thin film-based electronic device of any one of Embodiments149-152, wherein the thin film-based energy harvesting device furthercomprises an electron transport layer.

154. The thin film-based electronic device of any one of Embodiments149-153, wherein the thin film-based energy harvesting device furthercomprises a hole transport layer.

155. The thin film-based electronic device of any one of any one ofEmbodiments 144 to 154, wherein the thin-film based energy harvestingdevice is on one of the first current collector layer or the secondcurrent collector layer.

156. The thin film-based electronic device of Embodiment 155, whereinthe thin film-based electronic device further comprises a second thinfilm-based energy harvesting device on the other of the first currentcollector or the second current collector layer.

157. The thin film-based electronic device of Embodiment 156, whereinthe thin film-based energy harvesting device and the second thinfilm-based energy harvesting device are electrically serially connected.

158. The thin film-based electronic device of Embodiment 156, whereinthe thin film-based energy harvesting device and the second thinfilm-based energy harvesting device are electrically serially connectedthrough a diode therebetween.

159. The thin film-based electronic device of Embodiment 158, whereinthe diode is configured to be forward-biased when the thin film-basedESD is charging and reverse-biased when the thin film-based ESD isdischarging.

160. The thin film-based electronic device of Embodiment 156, furthercomprising a conductive layer over one or both of the thin film-basedenergy harvesting device and the second thin film-based energyharvesting device.

161. A wearable thin film-based electronic device comprising:

-   -   a plurality of laterally adjacent and electrically separated        current collectors over an electrically insulating substrate;        and    -   a plurality of electrically connected energy storage cells,    -   wherein each of the energy storage cells comprises a first        electrode layer of a first type on one of the current        collectors, a second electrode layer of a second type on an        adjacent one of the current collectors, and a separator        contacting and electrically separating the first electrode layer        and the second electrode layer, and    -   wherein the plurality of electrically connected energy storage        cells is configured to be worn by a user.

162. The wearable thin film-based electronic device of Embodiment 161,wherein adjacent ones of the energy storage cells share a common currentcollector layer having thereon the first electrode layer of a first oneof the adjacent ones of the energy storage cells and the secondelectrode layer of the second one of the adjacent ones of the energystorage cells.

163. The wearable thin film-based electronic device of Embodiments 161or 162, wherein the plurality of current collectors comprises a firstcurrent collector configured to serve as a current collector of a firstpolarity, a second current collector configured to serve as a currentcollector of a second polarity, and one or more intermediate currentcollectors configured to electrically connect the adjacent ones of theenergy storage cells.

164. The wearable thin film-based electronic device of any one ofEmbodiments 161-163, wherein each of the intermediate current collectorshas thereon one of the first electrode layers and one of the secondelectrode layers that are not electrically separated by one of theseparator layers.

165. The wearable thin film-based electronic device of any one ofEmbodiments 161-164, wherein each of the energy storage cells comprisesone of the first electrode layers having a first electrode activematerial and one of the second electrode layers having a secondelectrode active material, wherein a molar ratio between the firstelectrode active material and the second electrode active material isbetween 0.25 and 4.0.

166. The wearable thin film-based electronic device of Embodiment 165,wherein each of the energy storage cells has a ratio between a lateralarea of the first electrode layer and a lateral area of the secondelectrode that is proportional to the molar ratio.

167. The wearable thin film-based electronic device of any one ofEmbodiments 161-166, wherein in each of the energy storage cells, theseparator contacts top surfaces of the first electrode layer and thesecond electrode layer.

168. The wearable thin film-based electronic device of any one ofEmbodiments 161-166, wherein in each of the energy storage cells, theseparator is over the first electrode layer and the second electrodelayer is over the separator.

169. The wearable thin film-based electronic device of Embodiment 168,wherein the second electrode layer of a first one of the energy storagecells comprises a base portion extending from the adjacent one of thecurrent collectors in a vertical direction and a lateral extensionportion laterally extending from the base portion in the lateraldirection to overlap the first electrode layer on the one of the currentcollectors.

170. The wearable thin film-based electronic device of any one ofEmbodiments 161-169, wherein the plurality of current collectors arealong a line.

171. The wearable thin film-based electronic device of any one ofEmbodiments 161-170, wherein the plurality of current collector compriseconcentric layers.

172. The wearable thin film-based electronic device of any one ofEmbodiments 161-171, wherein the energy storage device is flexible.

173. The wearable thin film-based energy storage device of any one ofEmbodiments 161-172, wherein the wearable thin film-based electronicdevice is configured to be worn by a user as a wearable bracelet.

174. The wearable thin film-based energy storage device of any one ofEmbodiments 161-173, further comprising a core device powered by theplurality of electrically connected energy storage cells.

175. The wearable thin film-based energy storage device Embodiment 174,wherein the core device comprises a device selected from the groupconsisting of a light emitting device, an active or passive radiofrequency identification device, a Bluetooth® device, a sensor, aninfrared (IR) device, interface electronics, a Zigbee®-based device, anear-field communication (NFC)-based device, a health indicator monitorand a location tracking device.

176. A configurable energy storage device. comprising:

-   -   a plurality of laterally adjacent and electrically separated        current collectors over an electrically insulating substrate,    -   wherein the energy storage device comprises a plurality of        electrically connected energy storage cells, and    -   wherein the electrically connected energy storage cells are        configured to be detached from each other upon receiving a        mechanical force to form a pattern of electrically connected        energy storage cells.

177. The configurable energy storage device of Embodiment 176, whereineach of the energy storage cells comprises a first electrode layer of afirst type on one of the current collectors, a second electrode layer ofa second type on an adjacent one of the current collectors, and aseparator contacting and electrically separating the first electrodelayer and the second electrode layer.

178. The configurable energy storage device of Embodiments 176 or 177,wherein the plurality of electrically connected energy storage cells areconfigured to be detached at boundaries between adjacent ones of theplurality of electrically connected energy storage cells, wherein theboundaries comprise weakened structures in the electrically insulatingsubstrate that are adapted for separation upon receiving the mechanicalforce.

179. The configurable energy storage device of any one of Embodiment 176to 178, wherein the plurality of electrically connected energy storagecells are arranged as one or more rows of electrically connected energystorage cells and one or more columns of electrically connected energystorage cells.

180. The configurable energy storage device of any one of Embodiment179, wherein each of the one or more rows of electrically connectedenergy storage cells are electrically connected in series, and whereineach of the one or more columns of electrically connected energy storagecells are electrically connected in parallel.

181. An energy storage device comprising:

-   -   a plurality of radially arranged and electrically separated        current collectors over an electrically insulating substrate,    -   wherein the energy storage device comprises a plurality of        radially arranged and electrically connected energy storage        cells, and    -   wherein each of the energy storage cells comprises a first        electrode layer of a first type on one of the current        collectors, a second electrode layer of a second type on an        adjacent one of the current collectors, and a separator        contacting and electrically separating the first electrode layer        and the second electrode layer.

182. The energy storage device of Embodiment 181, wherein adjacent onesof the energy storage cells share a common current collector layerhaving thereon the first electrode layer of a first one of the adjacentones of the energy storage cells and the second electrode layer of thesecond one of the adjacent ones of the energy storage cells.

183. The energy storage device of Embodiments 181 or 182, wherein theplurality of current collectors comprises a first current collectorconfigured to serve as a current collector of a first polarity, a secondcurrent collector configured to serve as a current collector of a secondpolarity, and one or more intermediate current collectors configured toelectrically connect the adjacent ones of the energy storage cells.

184. The energy storage device of any one of Embodiments 181-183,wherein each of the intermediate current collectors has thereon one ofthe first electrode layers and one of the second electrode layers thatare not electrically separated by one of the separator layers.

185. The energy storage device of any one of Embodiments 181-184,wherein each of the energy storage cells comprises one of the firstelectrode layers having a first electrode active material and one of thesecond electrode layers having a second electrode active material,wherein a molar ratio between the first electrode active material andthe second electrode active material is between 0.25 and 4.0.

186. An energy storage device comprising:

-   -   an electrically insulating substrate;    -   a first current collector over the electrically insulating        substrate, wherein the first current collector comprises a        plurality of first current collector finger structures;    -   a second current collector over the electrically insulating        substrate, wherein the second current collector comprises a        plurality of second current collector finger structures, wherein        the first current collector finger structures and the second        current collector finger structures are interleaved to alternate        in a lateral direction,    -   wherein the first and second current collectors are radially        arranged such that one of the first and second current        collectors radially surrounds the other of the first and second        current collectors;    -   a first electrode layer of a first type over the first current        collector layer;    -   a second electrode layer of a second type over the second        current collector layer; and    -   a separator layer separating the first electrode layer and the        second electrode layer.

187. The energy storage device of Embodiment 186, wherein the firstelectrode layer comprises a first electrode active material and thesecond electrode layer comprises a second electrode active material,wherein a molar ratio between the first electrode active material andthe second electrode active material is between 0.25 and 4.0.

188. The energy storage device of Embodiments 186 or 187, wherein thefirst electrode layer comprises a first electrode active material andthe second electrode layer comprises a second electrode active material,wherein a ratio between a lateral area of the first electrode layer anda lateral area of the second electrode is proportional to the molarratio.

189. The energy storage device of any one of Embodiments 186-188,wherein the first electrode layer comprises a plurality of firstelectrode finger structures and the second electrode layer comprises aplurality of second electrode finger structures, and wherein the firstelectrode finger structures and the second electrode finger structuresare interleaved to alternate in the lateral direction.

190. The energy storage device of Embodiment 189, wherein the separatorlayer is over the first electrode layer and the second electrode layer.

191. The energy storage device of Embodiment 190, wherein the separatorlayer is interposed between adjacent pairs of the first electrode fingerstructures and the second electrode finger structures that alternate inthe lateral direction.

192. The energy storage device of Embodiment 191, wherein the separatorlayer is interposed between adjacent pairs of the first currentcollector finger structures and the second current collector fingerstructures that alternate in the lateral direction.

193. The energy storage device of any one of Embodiments 186-192,wherein the first electrode layer comprises a plurality of firstelectrode finger structures, wherein the separator layer is over each ofthe first electrode finger structures, and wherein the second electrodelayer is over the separator layer.

194. The energy storage device of Embodiment 193, wherein the separatorseparates the first electrode finger structures from the secondelectrode layer in the lateral direction and in the a verticaldirection.

195. The energy storage device of Embodiment 194, wherein the separatorlayer is interposed between adjacent pairs of the first currentcollector finger structures and the second current collector fingerstructures that alternate in the lateral direction.

196. The energy storage device of any one of Embodiments 186-195,wherein each of the first current collector finger structures and thesecond current collector finger structures has a ratio of a length to awidth between about 2 and 100.

197. The method of any one of Embodiments 1-20, the method of any one ofEmbodiments 21-36, the manufacturing kit of any one of Embodiments37-41, the method of fabricating an electrical system of any one ofEmbodiments 42-46, the energy storage device of any one of Embodiments47-54, the energy storage device of any one of Embodiments 55-75, theenergy storage device of any one of Embodiments 76-82, the energystorage device of any one of Embodiments 83-93, the energy storagedevice of any one of Embodiments 94-112, the method of any one ofEmbodiments 113-117, the thin-film-based electronic device of any one ofEmbodiments 118-142, the thin film-based electronic device of any one ofEmbodiments 143-160, the wearable thin film-based electronic device ofany one of Embodiments 161-175, the configurable energy storage deviceof any one of Embodiments 176-180, the energy storage device of any oneof Embodiments 181-185, or the energy storage device of any one ofEmbodiments 186-196, wherein the energy storage device further comprisesa non-aqueous electrolyte.

198. The method or device of Embodiment 197, wherein the non-aqueouselectrolyte comprises an organic electrolyte based on acetonitrile,propylene carbonate, ethylene carbonate, diethyl carbonate, dimethylcarbonate, ethyl acetate, 1,1,1,3,3,3-hexafluoropropan-2-ol,adiponitrile, 1,3-propylene sulfite, butylene carbonate,γ-butyrolactone, γ-valerolactone, propionitrile, glutaronitrile,adiponitrile, methoxyacetonitrile, 3-methoxypropionitrile,N,N-dimethylformamide, N,N-dimethylacetamide, N-methylpyrrolidinone,N-methyloxazolidinone, N,N″-dimethylimidazolininone, nitromethane,nitroethane, sulfonate, 3-methylsulfonate, dimethylsulfoxide, trimethylphosphate, or a combination thereof.

199. The method or device of Embodiments 197 or 198, wherein thenon-aqueous electrolyte comprises an ionic liquid.

200. The method or device of Embodiment 199, wherein a cation of theionic liquid comprises one or more of butyltrimethylammonium,1-ethyl-3-methylimidazolium, 1-butyl-3-methylimidazolium,1-methyl-3-propylimidazolium, 1-hexyl-3-methylimidazolium, choline,ethylammonium, tributylmethylphosphonium,tributyl(tetradecyl)phosphonium, trihexyl(tetradecyl)phosphonium,1-ethyl-2,3-methylimidazolium, 1-butyl-1-methylpiperidinium,diethylmethylsulfonium, 1-methyl-3-propylimidazolium,1-ethyl-3-methylimidazolium, 1-methyl-1-propylpiperidinium,1-butyl-2-methylpyridinium, 1-butyl-4-methylpyridinium,1-butyl-1-methylpyrrolidinium, diethylmethylsulfonium, or a combinationthereof.

201. The method or device of Embodiments 199 or 200, wherein an anion ofthe ionic liquid comprises one or more oftris(pentafluoroethyl)trifluorophosphate, trifluoromethanesulfonate,hexafluorophosphate, tetrafluoroborate, ethyl sulfate, dimethylphosphate, trifluoromethanesulfonate, methansulfonate, triflate,tricyanomethanide, dibutylphosphate, bis(trifluoromethylsulfonyl)imide,bis-2,4,4-(trimethylpentyl) phosphinate, iodides, chlorides, bromides,nitrates, or a combination thereof.

202. The method or device of any one of Embodiments 197-201, wherein thenon-aqueous electrolyte comprises an acid selected from the groupconsisting of H₂SO₄, HCl, HNO₃, HClO₄ and a combination thereof.

203. The method or device of any one of Embodiments 197-202, wherein thenon-aqueous electrolyte comprises a base selected from the groupconsisting of KOH, NaOH, LiOH, NH₄OH and a combination thereof.

204. The method or device of any one of Embodiments 197-203, wherein thenon-aqueous electrolyte comprises an inorganic-based salt selected fromthe group consisting of LiCl, Li₂SO₄, LiClO₄, NaCl, Na₂SO₄, NaNO₃, KCl,K₂SO₄, KNO₃, Ca(NO₃)₂, MgSO₄, ZnCl₂, Zn(BF₄)₂, ZnNO₃ and a combinationthereof.

205. The method or device of any one of Embodiments 197-204, wherein thenon-aqueous electrolyte comprises a low viscosity additive selected fromthe group consisting of water, an alcohol, a lactone, an ether, aketone, an ester, a polyols, a glycerol, a polymeric polyol or glycol,tetramethyl urea, n-methylpyrrolidone, acetonitrile, tetrahydrofuran(THF), dimethyl formamide (DMF), N-methyl formamide (NMF), dimethylsulfoxide (DMSO), thionyl chloride, sulfuryl chloride and a combinationthereof.

206. The method or device of any one of Embodiments 197-205, wherein thenon-aqueous electrolyte comprises a surfactant selected from the groupconsisting of cetyl alcohol, stearyl alcohol, cetostearyl alcohol, oleylalcohol, polyoxyethylene glycol alkyl ether, octaethylene glycolmonododecyl ether, glucoside alkyl ether, decyl glucoside,polyoxyethylene glycol octylphenol ether, Triton® X-100, nonoxynol-9,glyceryl laurate, polysorbate, a poloxamer or a combination thereof.

207. The method or device of any one of Embodiment 197-206, wherein thenon-aqueous electrolyte comprises a polymer binder selected from thegroup consisting of polyvinyl pyrrolidone (PVP), polyvinyl alcohol(PVA), polyvinylidene fluoride, polyvynylidenefluoride-trifluoroethylene, polytetrafluoroethylene,polydimethylsiloxane, polyethelene, polypropylene, polyethylene oxide,polypropylene oxide, polyethylene glycolhexafluoropropylene,polyethylene terefphtalatpolyacrylonitryle, polyvinyl butyral,polyvinylcaprolactam, polyvinyl chloride, polyimide, polyamide,polyacrylamide, an acrylate polymer, a methacrylate polymer,acrylonitrile butadiene styrene, allylmethacrylate, polystyrene,polybutadiene, polybutylene terephthalate, polycarbonate,polychloroprene, polyethersulfone, nylon, styrene-acrylonitrile resin,polyethylene glycol, hectorite clay, garamite clay, an organo-modifiedclay, a saccharide, a polysaccharide, a cellulose, a modified celluloseand a combination thereof

208. The method of any one of Embodiments 1-20, the method of any one ofEmbodiments 21-36, the manufacturing kit of any one of Embodiments37-41, the method of fabricating an electrical system of any one ofEmbodiments 42-46, the energy storage device of any one of Embodiments47-54, the energy storage device of any one of Embodiments 55-75, theenergy storage device of any one of Embodiments 76-82, the energystorage device of any one of Embodiments 83-93, the energy storagedevice of any one of Embodiments 94-112, the method of any one ofEmbodiments 113-117, the thin-film-based electronic device of any one ofEmbodiments 118-142, the thin film-based electronic device of any one ofEmbodiments 143-160, the wearable thin film-based electronic device ofany one of Embodiments 161-175, the configurable energy storage deviceof any one of Embodiments 176-180, the energy storage device of any oneof Embodiments 181-185, or the energy storage device of any one ofEmbodiments 186-196, wherein the separator comprises a filler materialcomprising one or more of diatom frustules, a zeolite, cellulose fibers,fiberglass, alumina, silica gel, molecular sieve carbon, a natural-claybased solid, a polymeric absorbent or a combination thereof.

209. The method of any one of Embodiments 1-20, the method of any one ofEmbodiments 21-36, the manufacturing kit of any one of Embodiments37-41, the method of fabricating an electrical system of any one ofEmbodiments 42-46, the energy storage device of any one of Embodiments47-54, the energy storage device of any one of Embodiments 55-75, theenergy storage device of any one of Embodiments 76-82, the energystorage device of any one of Embodiments 83-93, the energy storagedevice of any one of Embodiments 94-112, the method of any one ofEmbodiments 113-117, the thin-film-based electronic device of any one ofEmbodiments 118-142, the thin film-based electronic device of any one ofEmbodiments 143-160, the wearable thin film-based electronic device ofany one of Embodiments 161-175, the configurable energy storage deviceof any one of Embodiments 176-180, the energy storage device of any oneof Embodiments 181-185, or the energy storage device of any one ofEmbodiments 186-196, wherein one of the first electrode layer or thesecond electrode layer comprises a cathode electrode active materialcomprising a silver-containing compound or a manganese-containingcompound.

210. The method of any one of Embodiments 1-20, the method of any one ofEmbodiments 21-36, the manufacturing kit of any one of Embodiments37-41, the method of fabricating an electrical system of any one ofEmbodiments 42-46, the energy storage device of any one of Embodiments47-54, the energy storage device of any one of Embodiments 55-75, theenergy storage device of any one of Embodiments 76-82, the energystorage device of any one of Embodiments 83-93, the energy storagedevice of any one of Embodiments 94-112, the method of any one ofEmbodiments 113-117, the thin-film-based electronic device of any one ofEmbodiments 118-142, the thin film-based electronic device of any one ofEmbodiments 143-160, the wearable thin film-based electronic device ofany one of Embodiments 161-175, the configurable energy storage deviceof any one of Embodiments 176-180, the energy storage device of any oneof Embodiments 181-185, or the energy storage device of any one ofEmbodiments 186-196, wherein one of the first electrode layer or thesecond electrode layer comprises a cathode electrode active materialcomprises a silver(I) oxide (Ag₂O), silver(I,III) oxide (AgO), a mixturecomprising silver(I) oxide (Ag₂O) and manganese(IV) oxide (MnO₂), amanganese (II, III) oxide (Mn₃O₄), a manganese (II) oxide (MnO), amanganese (III) oxide (Mn₂O₃), a manganese oxyhydroxide (MnOOH), amixture comprising silver(I) oxide (Ag₂O) and nickel oxyhydroxide(NiOOH), silver nickel oxide (AgNiO₂) or a combination thereof.

211. The method of any one of Embodiments 1-20, the method of any one ofEmbodiments 21-36, the manufacturing kit of any one of Embodiments37-41, the method of fabricating an electrical system of any one ofEmbodiments 42-46, the energy storage device of any one of Embodiments47-54, the energy storage device of any one of Embodiments 55-75, theenergy storage device of any one of Embodiments 76-82, the energystorage device of any one of Embodiments 83-93, the energy storagedevice of any one of Embodiments 94-112, the method of any one ofEmbodiments 113-117, the thin-film-based electronic device of any one ofEmbodiments 118-142, the thin film-based electronic device of any one ofEmbodiments 143-160, the wearable thin film-based electronic device ofany one of Embodiments 161-175, the configurable energy storage deviceof any one of Embodiments 176-180, the energy storage device of any oneof Embodiments 181-185, or the energy storage device of any one ofEmbodiments 186-196, wherein one of the first electrode layer or thesecond electrode layer comprises an anode electrode active materialselected from the group consisting of zinc, cadmium, iron, nickel,aluminum, metal hydrate, hydrogen or a combinations thereof.

212. The method of any one of Embodiments 1-20, the method of any one ofEmbodiments 21-36, the manufacturing kit of any one of Embodiments37-41, the method of fabricating an electrical system of any one ofEmbodiments 42-46, the energy storage device of any one of Embodiments47-54, the energy storage device of any one of Embodiments 55-75, theenergy storage device of any one of Embodiments 76-82, the energystorage device of any one of Embodiments 83-93, the energy storagedevice of any one of Embodiments 94-112, the method of any one ofEmbodiments 113-117, the thin-film-based electronic device of any one ofEmbodiments 118-142, the thin film-based electronic device of any one ofEmbodiments 143-160, the wearable thin film-based electronic device ofany one of Embodiments 161-175, the configurable energy storage deviceof any one of Embodiments 176-180, the energy storage device of any oneof Embodiments 181-185, or the energy storage device of any one ofEmbodiments 186-196, wherein the energy storage device comprises azinc/carbon primary battery, a zinc/alkaline/manganese primary battery,a magnesium/manganese dioxide primary battery, a zinc/mercuric oxideprimary battery, a cadmium/mercuric oxide primary battery, a zinc/silveroxide primary battery, a zinc/air primary battery, a lithium/solublecathode primary battery or a lithium/solid cathode primary battery.

213. The method of any one of Embodiments 1-20, the method of any one ofEmbodiments 21-36, the manufacturing kit of any one of Embodiments37-41, the method of fabricating an electrical system of any one ofEmbodiments 42-46, the energy storage device of any one of Embodiments47-54, the energy storage device of any one of Embodiments 55-75, theenergy storage device of any one of Embodiments 76-82, the energystorage device of any one of Embodiments 83-93, the energy storagedevice of any one of Embodiments 94-112, the method of any one ofEmbodiments 113-117, the thin-film-based electronic device of any one ofEmbodiments 118-142, the thin film-based electronic device of any one ofEmbodiments 143-160, the wearable thin film-based electronic device ofany one of Embodiments 161-175, the configurable energy storage deviceof any one of Embodiments 176-180, the energy storage device of any oneof Embodiments 181-185, or the energy storage device of any one ofEmbodiments 186-196, wherein the energy storage device comprises anickel/iron secondary battery, a silver/iron secondary battery, aniron/air secondary battery, a nickel/cadmium secondary battery, anickel/metal hydride secondary battery, a nickel/zinc secondary battery,a zinc/silver oxide secondary battery, a lithium-ion secondary battery,a lithium/metal secondary battery, a Zn/MnO₂ secondary battery, azinc/air secondary battery, an aluminum/air secondary battery, amagnesium/air secondary battery or a lithium/air/lithium/polymersecondary battery.

214. The method of any one of Embodiments 1-20, the method of any one ofEmbodiments 21-36, the manufacturing kit of any one of Embodiments37-41, the method of fabricating an electrical system of any one ofEmbodiments 42-46, the energy storage device of any one of Embodiments47-54, the energy storage device of any one of Embodiments 55-75, theenergy storage device of any one of Embodiments 76-82, the energystorage device of any one of Embodiments 83-93, the energy storagedevice of any one of Embodiments 94-112, the method of any one ofEmbodiments 113-117, the thin-film-based electronic device of any one ofEmbodiments 118-142, the thin film-based electronic device of any one ofEmbodiments 143-160, the wearable thin film-based electronic device ofany one of Embodiments 161-175, the configurable energy storage deviceof any one of Embodiments 176-180, the energy storage device of any oneof Embodiments 181-185, or the energy storage device of any one ofEmbodiments 186-196, wherein the energy storage device comprises asupercapacitor.

215. The method of any one of Embodiments 1-20, the method of any one ofEmbodiments 21-36, the manufacturing kit of any one of Embodiments37-41, the method of fabricating an electrical system of any one ofEmbodiments 42-46, the energy storage device of any one of Embodiments47-54, the energy storage device of any one of Embodiments 55-75, theenergy storage device of any one of Embodiments 76-82, the energystorage device of any one of Embodiments 83-93, the energy storagedevice of any one of Embodiments 94-112, the method of any one ofEmbodiments 113-117, the thin-film-based electronic device of any one ofEmbodiments 118-142, the thin film-based electronic device of any one ofEmbodiments 143-160, the wearable thin film-based electronic device ofany one of Embodiments 161-175, the configurable energy storage deviceof any one of Embodiments 176-180, the energy storage device of any oneof Embodiments 181-185, or the energy storage device of any one ofEmbodiments 186-196, wherein the energy storage device comprises asupercapacitor, wherein each of the first and second electrode layerscomprises an electric double-layer capacitor.

216. The method of any one of Embodiments 1-20, the method of any one ofEmbodiments 21-36, the manufacturing kit of any one of Embodiments37-41, the method of fabricating an electrical system of any one ofEmbodiments 42-46, the energy storage device of any one of Embodiments47-54, the energy storage device of any one of Embodiments 55-75, theenergy storage device of any one of Embodiments 76-82, the energystorage device of any one of Embodiments 83-93, the energy storagedevice of any one of Embodiments 94-112, the method of any one ofEmbodiments 113-117, the thin-film-based electronic device of any one ofEmbodiments 118-142, the thin film-based electronic device of any one ofEmbodiments 143-160, the wearable thin film-based electronic device ofany one of Embodiments 161-175, the configurable energy storage deviceof any one of Embodiments 176-180, the energy storage device of any oneof Embodiments 181-185, or the energy storage device of any one ofEmbodiments 186-196, wherein the energy storage device comprises asupercapacitor, wherein each of the first and second electrode layerscomprises a pseudo capacitor.

217. The method of any one of Embodiments 1-20, the method of any one ofEmbodiments 21-36, the manufacturing kit of any one of Embodiments37-41, the method of fabricating an electrical system of any one ofEmbodiments 42-46, the energy storage device of any one of Embodiments47-54, the energy storage device of any one of Embodiments 55-75, theenergy storage device of any one of Embodiments 76-82, the energystorage device of any one of Embodiments 83-93, the energy storagedevice of any one of Embodiments 94-112, the method of any one ofEmbodiments 113-117, the thin-film-based electronic device of any one ofEmbodiments 118-142, the thin film-based electronic device of any one ofEmbodiments 143-160, the wearable thin film-based electronic device ofany one of Embodiments 161-175, the configurable energy storage deviceof any one of Embodiments 176-180, the energy storage device of any oneof Embodiments 181-185, or the energy storage device of any one ofEmbodiments 186-196, wherein the energy storage device comprises ahybrid supercapacitor, wherein the first electrode layer configured asan electric double-layer capacitor and a second electrode layerconfigured as an electric double-layer capacitor.

218. The method of any one of Embodiments 1-20, the method of any one ofEmbodiments 21-36, the manufacturing kit of any one of Embodiments37-41, the method of fabricating an electrical system of any one ofEmbodiments 42-46, the energy storage device of any one of Embodiments47-54, the energy storage device of any one of Embodiments 55-75, theenergy storage device of any one of Embodiments 76-82, the energystorage device of any one of Embodiments 83-93, the energy storagedevice of any one of Embodiments 94-112, the method of any one ofEmbodiments 113-117, the thin-film-based electronic device of any one ofEmbodiments 118-142, the thin film-based electronic device of any one ofEmbodiments 143-160, the wearable thin film-based electronic device ofany one of Embodiments 161-175, the configurable energy storage deviceof any one of Embodiments 176-180, the energy storage device of any oneof Embodiments 181-185, or the energy storage device of any one ofEmbodiments 186-196, wherein the energy storage device comprises asupercapacitor having symmetric electrodes, wherein each of the firstand second electrode layers comprises a zinc oxide (Zn_(x)O_(y)) or amanganese oxide (Mn_(x)O_(y)).

219. The method of any one of Embodiments 1-20, the method of any one ofEmbodiments 21-36, the manufacturing kit of any one of Embodiments37-41, the method of fabricating an electrical system of any one ofEmbodiments 42-46, the energy storage device of any one of Embodiments47-54, the energy storage device of any one of Embodiments 55-75, theenergy storage device of any one of Embodiments 76-82, the energystorage device of any one of Embodiments 83-93, the energy storagedevice of any one of Embodiments 94-112, the method of any one ofEmbodiments 113-117, the thin-film-based electronic device of any one ofEmbodiments 118-142, the thin film-based electronic device of any one ofEmbodiments 143-160, the wearable thin film-based electronic device ofany one of Embodiments 161-175, the configurable energy storage deviceof any one of Embodiments 176-180, the energy storage device of any oneof Embodiments 181-185, or the energy storage device of any one ofEmbodiments 186-196, wherein the energy storage device comprises asupercapacitor having symmetric electrodes, wherein each of the firstand second electrode layers comprises carbon nanotubes.

220. The method of any one of Embodiments 1-20, the method of any one ofEmbodiments 21-36, the manufacturing kit of any one of Embodiments37-41, the method of fabricating an electrical system of any one ofEmbodiments 42-46, the energy storage device of any one of Embodiments47-54, the energy storage device of any one of Embodiments 55-75, theenergy storage device of any one of Embodiments 76-82, the energystorage device of any one of Embodiments 83-93, the energy storagedevice of any one of Embodiments 94-112, the method of any one ofEmbodiments 113-117, the thin-film-based electronic device of any one ofEmbodiments 118-142, the thin film-based electronic device of any one ofEmbodiments 143-160, the wearable thin film-based electronic device ofany one of Embodiments 161-175, the configurable energy storage deviceof any one of Embodiments 176-180, the energy storage device of any oneof Embodiments 181-185, or the energy storage device of any one ofEmbodiments 186-196, wherein the energy storage device comprises asupercapacitor having asymmetric electrodes, wherein one of the firstand second electrode layers comprises a zinc oxide (Zn_(x)O_(y)) or amanganese oxide (Mn_(x)O_(y)) and the other of the first and secondelectrode layers comprises carbon nanotubes.

Unless the context clearly requires otherwise, throughout thedescription and the claims, the words “comprise,” “comprising,”“include,” “including” and the like are to be construed in an inclusivesense, as opposed to an exclusive or exhaustive sense; that is to say,in the sense of “including, but not limited to.” The word “coupled”, asgenerally used herein, refers to two or more elements that may be eitherdirectly connected, or connected by way of one or more intermediateelements. Likewise, the word “connected”, as generally used herein,refers to two or more elements that may be either directly connected, orconnected by way of one or more intermediate elements. Additionally, thewords “herein,” “above,” “below,” and words of similar import, when usedin this application, shall refer to this application as a whole and notto any particular portions of this application. Where the contextpermits, words in the above Detailed Description using the singular orplural number may also include the plural or singular number,respectively. The word “or” in reference to a list of two or more items,that word covers all of the following interpretations of the word: anyof the items in the list, all of the items in the list, and anycombination of the items in the list.

Moreover, conditional language used herein, such as, among others,“can,” “could,” “might,” “may,” “e.g.,” “for example,” “such as” and thelike, unless specifically stated otherwise, or otherwise understoodwithin the context as used, is generally intended to convey that certainembodiments include, while other embodiments do not include, certainfeatures, elements and/or states. Thus, such conditional language is notgenerally intended to imply that features, elements and/or states are inany way required for one or more embodiments or whether these features,elements and/or states are included or are to be performed in anyparticular embodiment.

While certain embodiments have been described, these embodiments havebeen presented by way of example only, and are not intended to limit thescope of the disclosure. Indeed, the novel apparatus, methods, andsystems described herein may be embodied in a variety of other forms;furthermore, various omissions, substitutions and changes in the form ofthe methods and systems described herein may be made without departingfrom the spirit of the disclosure. For example, while blocks arepresented in a given arrangement, alternative embodiments may performsimilar functionalities with different components and/or circuittopologies, and some blocks may be deleted, moved, added, subdivided,combined, and/or modified. Each of these blocks may be implemented in avariety of different ways. Any suitable combination of the elements andacts of the various embodiments described above can be combined toprovide further embodiments. The various features and processesdescribed above may be implemented independently of one another, or maybe combined in various ways. All possible combinations andsubcombinations of features of this disclosure are intended to fallwithin the scope of this disclosure.

In addition, unless otherwise specified, none of the steps of themethods of the present disclosure are confined to any particular orderof performance. Modifications of the disclosed examples incorporatingthe spirit and substance of the disclosure may occur to persons skilledin the art and such modifications are within the scope of the presentdisclosure. Furthermore, all references cited herein are incorporated byreference in their entirety.

While the methods and devices described herein may be susceptible tovarious modifications and alternative forms, specific examples thereofhave been shown in the drawings and are herein described in detail. Itshould be understood, however, that the invention is not to be limitedto the particular forms or methods disclosed, but, to the contrary, theinvention is to cover all modifications, equivalents, and alternativesfalling within the spirit and scope of the various examples describedand the appended claims. Further, the disclosure herein of anyparticular feature, aspect, method, property, characteristic, quality,attribute, element, or the like in connection with an example can beused in all other examples set forth herein. Any methods disclosedherein need not be performed in the order recited. Depending on theexample, one or more acts, events, or functions of any of thealgorithms, methods, or processes described herein can be performed in adifferent sequence, can be added, merged, or left out altogether (e.g.,not all described acts or events are necessary for the practice of themethod). In some examples, acts or events can be performed concurrently.Further, no element, feature, block, or step, or group of elements,features, blocks, or steps, are necessary or indispensable to eachexample. Additionally, all possible combinations, subcombinations, andrearrangements of systems, methods, features, elements, modules, blocks,and so forth are within the scope of this disclosure. The use ofsequential, or time-ordered language, such as “then,” “next,” “after,”“subsequently,” and the like, unless specifically stated otherwise, orotherwise understood within the context as used, is generally intendedto facilitate the flow of the text and is not intended to limit thesequence of operations performed. Thus, some examples may be performedusing the sequence of operations described herein, while other examplesmay be performed following a different sequence of operations.

The ranges disclosed herein also encompass any and all overlap,sub-ranges, and combinations thereof. Language such as “up to,” “atleast,” “greater than,” “less than,” “between,” and the like includesthe number recited. Numbers preceded by a term such as “about” or“approximately” include the recited numbers and should be interpretedbased on the circumstances (e.g., as accurate as reasonably possibleunder the circumstances, for example ±5%, ±10%, ±15%, etc.). Forexample, “about 1 V” includes “1 V.” Numbers not preceded by a term suchas “about” or “approximately” may be understood to based on thecircumstances to be as accurate as reasonably possible under thecircumstances, for example ±5%, ±10%, ±15%, etc. For example, “1 V”includes “0.9-1.1 V.” Phrases preceded by a term such as “substantially”include the recited phrase and should be interpreted based on thecircumstances (e.g., as much as reasonably possible under thecircumstances). For example, “substantially perpendicular” includes“perpendicular.” Unless stated otherwise, all measurements are atstandard conditions including temperature and pressure. The phrase “atleast one of” is intended to require at least one item from thesubsequent listing, not one type of each item from each item in thesubsequent listing. For example, “at least one of A, B, and C” caninclude A, B, C, A and B, A and C, B and C, or A, B, and C.

What is claimed is:
 1. An energy storage device comprising: a firstcurrent collector layer and a second current collector layer adjacentlydisposed in a lateral direction over an electrically insulatingsubstrate; a first electrode layer of a first type over the firstcurrent collector layer; a separator over the first electrode layer; anda second electrode layer of a second type different from the first typecomprising a base portion extending from the second current collectorlayer in a vertical direction and a lateral extension portion extendingfrom the base portion in the lateral direction to overlap the firstelectrode layer, wherein one or more of the first current collectorlayer, the first electrode layer, the separator, the second electrodelayer and the second current collector layer comprises a printed layer.2. The energy storage device of claim 1, wherein the energy storagedevice is printed on the same side of the electrically insulatingsubstrate as a core device configured to be electrically powered by theenergy storage device.
 3. The energy storage device of claim 1, whereinthe electrically insulating substrate comprises a polymeric substrate.4. The energy storage device of claim 1, wherein the electricallyinsulating substrate comprises a flexible substrate.
 5. The energystorage device of claim 1, wherein the separator comprises: a verticalportion interposed in the lateral direction between the base portion ofthe second electrode layer and a side surface of the first electrodelayer; and a horizontal portion interposed in the vertical directionbetween the lateral extension portion of the second electrode layer andthe first electrode layer.
 6. The energy storage device of claim 1,wherein the base portion of the second electrode layer has a width thatis thicker than a thickness of the lateral extension portion of thesecond electrode layer.
 7. The energy storage device of claim 6, whereinthe width of the base portion of the second electrode layer is greaterthan the thickness of the lateral extension portion of the secondelectrode layer by a factor between two to ten.
 8. The energy storagedevice of claim 1, wherein the first electrode layer comprises a firstelectrode active material and the second electrode layer comprises asecond electrode active material, wherein a molar ratio between thefirst electrode active material and the second electrode active materialis between 0.25 and 4.0.
 9. An energy storage device comprising: anelectrically insulating substrate; a first current collector layer overthe electrically insulating substrate, wherein the first currentcollector layer comprises a plurality of first current collector fingerstructures; a second current collector layer over the electricallyinsulating substrate, wherein the second current collector layercomprises a plurality of second current collector finger structures,wherein the first current collector finger structures and the secondcurrent collector finger structures are interleaved to alternate in alateral direction; a first electrode layer of a first type over thefirst current collector layer; a second electrode layer of a second typeover the second current collector layer; and a separator layerseparating the first electrode layer and the second electrode layer. 10.The energy storage device of claim 9, wherein the energy storage deviceis printed on the same side of the electrically insulating substrate asa core device configured to be electrically powered by the energystorage device.
 11. The energy storage device of claim 9, wherein thefirst electrode layer comprises a first electrode active material andthe second electrode layer comprises a second electrode active material,wherein a molar ratio between the first electrode active material andthe second electrode active material is between 0.25 and 4.0.
 12. Theenergy storage device of claim 9, wherein the first electrode layercomprises a first electrode active material and the second electrodelayer comprises a second electrode active material, wherein a ratiobetween a lateral area of the first electrode layer and a lateral areaof the second electrode is proportional to the molar ratio.
 13. Theenergy storage device of claim 9, wherein the first electrode layercomprises a plurality of first electrode finger structures and thesecond electrode layer comprises a plurality of second electrode fingerstructures, and wherein the first electrode finger structures and thesecond electrode finger structures are interleaved to alternate in thelateral direction.
 14. The energy storage device of claim 13, whereinthe separator layer is over the first electrode layer and the secondelectrode layer.
 15. The energy storage device of claim 14, wherein theseparator layer is interposed between adjacent pairs of the firstelectrode finger structures and the second electrode finger structuresthat alternate in the lateral direction.
 16. The energy storage deviceof claim 15, wherein the separator layer is interposed between adjacentpairs of the first current collector finger structures and the secondcurrent collector finger structures that alternate in the lateraldirection.
 17. The energy storage device of claim 9, wherein the firstelectrode layer comprises a plurality of first electrode fingerstructures, wherein the separator layer is over each of the firstelectrode finger structures, and wherein the second electrode layer isover the separator layer.
 18. The energy storage device of claim 17,wherein the separator separates the first electrode finger structuresfrom the second electrode layer in the lateral direction and in the avertical direction.
 19. The energy storage device of claim 18, whereinthe separator layer is interposed between adjacent pairs of the firstcurrent collector finger structures and the second current collectorfinger structures that alternate in the lateral direction.
 20. Theenergy storage device of claim 9, wherein each of the first currentcollector finger structures and the second current collector fingerstructures has a ratio of a length to a width between about 2 and 100.